carcinogens and mutagens in ambient air particulate …
TRANSCRIPT
CADOHAIHLSP-35
CARCINOGENS AND MUTAGENS IN AMBIENT AIR PARTICULATE MATTER SOURCES AND TRENDS IN CONTRA COSTA COUNTY
Contract No ARB Al-162-32
Final Report
June 1985
Prepared by
P Flessel G Guirguis K Chang J Cheng J Lecocq W Lu K Liu and J Wesolowski
Air and Industrial Hygiene Laboratory California State Department of Health Services
2151 Berkeley Way Berkeley California 94704
and
N Kado Research Division
California Air Resources Board PO Box 2815
Sacramento California 95812
Prepared for California Air Resources Board Research Division PO Box 2815 Sacramento California 95812 Charles Unger Project Officer
The statements and conclusions in this report are those of
the Contractor and not necessarily those of the State Air
Resources Board The mention of commercial products their
source or their use in connection with material reported
herein is not to be construed as either an actual or implied
endorsement of such products
-ii-
ABSTRACT
Many mutagens and carcinogens are known to be present in urban community air
Extensive chemical and biological characterization of these atmospheric pollutants is
essential if accurate risk assessments are to be made and effective control strategies
developed This report describes progress in three areas of this complex environmental
problem 1 the development of more sensitive methods for measuring aerosol mutagens
2 the identification of sources of mutagens and 3 the analysis of trends in mutagen
and polycyclic aromatic hydrocarbon (PAH) levels in particulate organic matter (POM)
bull A highly sensitive version of the Ames Salmonella test called the microsuspension
test was applied to measure the mutagenic activity in organic extracts of community
aerosols Application of the microsuspension Ames test made possible high resolution
diurnal studies of mutagenicity in small air samples of only 2 hours duration Diurnal
variations in mutagenic density (revertantsm3) of more than a factor of 10 were
observed and these variations were highly correlated with fine fraction lead (Pb) in
a pilot field study The test can be applied in future studies were sample mass is
a limiting factor
bull The origins of mutagens in POM were investigated further by sampling in Contra
Costa County during six seasonal pollution episodes each of 36 hours duration in
1982-1984 Samples were collected at four locations (Richmond Martinez Concord
Pittsburg) and analyzed for mutagenic activity in the Ames test for PAH oxyanions
(N0 - so =) pollutant gases (CO NO N02
o3
so ) and elemental source tracers3 4 2
(including Pb Br Ni Fe and K) Diurnal geographic and seasonal comparisons
were made Statistical techniques including principal component (factor) analysis
were used to explore relationships between aerosol mutagens PAH and source tracers
The results confirmed earlier observations and provided some new insights into the
sources of aerosol mutagens
(i) Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
-iii-
a In this present and previous Contra Costa studies mutagenic density
and PAH were significantly positively correlated with fine fraction
( lt 25 micromd ) Pb andor Br both derived primarily from motor a
vehicles
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions as well as other combustion source particulate matter
c Studies of upwind-downwind freeway data in Los Angeles by Stateshy
wide Air Pollution Research Center (SAPRC) s~ientists have demonshy
strated an incremental burden of direct mutagens in aerosol attrishy
butable to freeway traffic The amount was comparable to the
area wide background mutagen density
(ii) Many results suggest that some mutagens behave as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is supported by the following evidence
a During pollutation episodes in Contra Costa County mutagens were
positively correlated with N03- assumed to be a secondary aerosol
tracer The association of mutagenicity with N0 occurred areashy3
-
wide
3b SAPRC scientists observed that ratios of mutagen densities (revm )
to CO were generally higher at Riverside California a downwind
receptor site than at El Monte an intermediate receptor site in
the Los Angeles basin Since CO is an unreactive combustion
emission the mutagen densityCO ratio takes into account variations
in emissions and atmospheric dispersion Higher ratios at Riverside
suggest atmospheric mutagen formation during aerosol transport
from Los Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study were highest
-iv-
during summer episodes when the prevailing atmospheric conditions
(ie hot dry stagnant) favored chemical transformations Since
Pb like CO is an unreacti ve emission the mutagenic densityPb
ratio should take into account variations in automotive emission
profiles and dispersion Thus the high ratios during episodes in
August 1981 and September 1983 may reflect atmospheric mutagen
formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH mutagens Mutagenicity of some nitro-PAHs exceed the
mutagenicity of the parent PAH by several orders of magnitude in
laboratory analysis Some of these highly mutagenic ni tro-PAHs are
known to be primary pollutants emitted by various combustion
sources However chamber studies have also shown that irradiation
of mixtures of atmospheric hydrocarbons nitric acid (HNO ) and3 reactive gases (NO2 o ) can lead to mutagen formation Thus3 some hydrocarbons may be converted to secondary mutagenic
products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likely
presence of nitroarene mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes and derivatives which are
not only ubiquitious primary pollutants but may also be derived
from secondary atmospheric transformations We infer that such
compounds were probably major contributors to the mutagenicity
of Contra Costa aerosols from the fact that mutagenic activities
of aerosol extracts were two to three times lower in a Salmonella
strain (T A98NR) deficient in an enzyme required for some monoshy
ni troarene activation than in the standard tester strain (T A98)
-v-
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
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11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
-59-
39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
-60-
48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
The statements and conclusions in this report are those of
the Contractor and not necessarily those of the State Air
Resources Board The mention of commercial products their
source or their use in connection with material reported
herein is not to be construed as either an actual or implied
endorsement of such products
-ii-
ABSTRACT
Many mutagens and carcinogens are known to be present in urban community air
Extensive chemical and biological characterization of these atmospheric pollutants is
essential if accurate risk assessments are to be made and effective control strategies
developed This report describes progress in three areas of this complex environmental
problem 1 the development of more sensitive methods for measuring aerosol mutagens
2 the identification of sources of mutagens and 3 the analysis of trends in mutagen
and polycyclic aromatic hydrocarbon (PAH) levels in particulate organic matter (POM)
bull A highly sensitive version of the Ames Salmonella test called the microsuspension
test was applied to measure the mutagenic activity in organic extracts of community
aerosols Application of the microsuspension Ames test made possible high resolution
diurnal studies of mutagenicity in small air samples of only 2 hours duration Diurnal
variations in mutagenic density (revertantsm3) of more than a factor of 10 were
observed and these variations were highly correlated with fine fraction lead (Pb) in
a pilot field study The test can be applied in future studies were sample mass is
a limiting factor
bull The origins of mutagens in POM were investigated further by sampling in Contra
Costa County during six seasonal pollution episodes each of 36 hours duration in
1982-1984 Samples were collected at four locations (Richmond Martinez Concord
Pittsburg) and analyzed for mutagenic activity in the Ames test for PAH oxyanions
(N0 - so =) pollutant gases (CO NO N02
o3
so ) and elemental source tracers3 4 2
(including Pb Br Ni Fe and K) Diurnal geographic and seasonal comparisons
were made Statistical techniques including principal component (factor) analysis
were used to explore relationships between aerosol mutagens PAH and source tracers
The results confirmed earlier observations and provided some new insights into the
sources of aerosol mutagens
(i) Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
-iii-
a In this present and previous Contra Costa studies mutagenic density
and PAH were significantly positively correlated with fine fraction
( lt 25 micromd ) Pb andor Br both derived primarily from motor a
vehicles
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions as well as other combustion source particulate matter
c Studies of upwind-downwind freeway data in Los Angeles by Stateshy
wide Air Pollution Research Center (SAPRC) s~ientists have demonshy
strated an incremental burden of direct mutagens in aerosol attrishy
butable to freeway traffic The amount was comparable to the
area wide background mutagen density
(ii) Many results suggest that some mutagens behave as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is supported by the following evidence
a During pollutation episodes in Contra Costa County mutagens were
positively correlated with N03- assumed to be a secondary aerosol
tracer The association of mutagenicity with N0 occurred areashy3
-
wide
3b SAPRC scientists observed that ratios of mutagen densities (revm )
to CO were generally higher at Riverside California a downwind
receptor site than at El Monte an intermediate receptor site in
the Los Angeles basin Since CO is an unreactive combustion
emission the mutagen densityCO ratio takes into account variations
in emissions and atmospheric dispersion Higher ratios at Riverside
suggest atmospheric mutagen formation during aerosol transport
from Los Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study were highest
-iv-
during summer episodes when the prevailing atmospheric conditions
(ie hot dry stagnant) favored chemical transformations Since
Pb like CO is an unreacti ve emission the mutagenic densityPb
ratio should take into account variations in automotive emission
profiles and dispersion Thus the high ratios during episodes in
August 1981 and September 1983 may reflect atmospheric mutagen
formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH mutagens Mutagenicity of some nitro-PAHs exceed the
mutagenicity of the parent PAH by several orders of magnitude in
laboratory analysis Some of these highly mutagenic ni tro-PAHs are
known to be primary pollutants emitted by various combustion
sources However chamber studies have also shown that irradiation
of mixtures of atmospheric hydrocarbons nitric acid (HNO ) and3 reactive gases (NO2 o ) can lead to mutagen formation Thus3 some hydrocarbons may be converted to secondary mutagenic
products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likely
presence of nitroarene mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes and derivatives which are
not only ubiquitious primary pollutants but may also be derived
from secondary atmospheric transformations We infer that such
compounds were probably major contributors to the mutagenicity
of Contra Costa aerosols from the fact that mutagenic activities
of aerosol extracts were two to three times lower in a Salmonella
strain (T A98NR) deficient in an enzyme required for some monoshy
ni troarene activation than in the standard tester strain (T A98)
-v-
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
-56-
11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
-59-
39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
-60-
48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
ABSTRACT
Many mutagens and carcinogens are known to be present in urban community air
Extensive chemical and biological characterization of these atmospheric pollutants is
essential if accurate risk assessments are to be made and effective control strategies
developed This report describes progress in three areas of this complex environmental
problem 1 the development of more sensitive methods for measuring aerosol mutagens
2 the identification of sources of mutagens and 3 the analysis of trends in mutagen
and polycyclic aromatic hydrocarbon (PAH) levels in particulate organic matter (POM)
bull A highly sensitive version of the Ames Salmonella test called the microsuspension
test was applied to measure the mutagenic activity in organic extracts of community
aerosols Application of the microsuspension Ames test made possible high resolution
diurnal studies of mutagenicity in small air samples of only 2 hours duration Diurnal
variations in mutagenic density (revertantsm3) of more than a factor of 10 were
observed and these variations were highly correlated with fine fraction lead (Pb) in
a pilot field study The test can be applied in future studies were sample mass is
a limiting factor
bull The origins of mutagens in POM were investigated further by sampling in Contra
Costa County during six seasonal pollution episodes each of 36 hours duration in
1982-1984 Samples were collected at four locations (Richmond Martinez Concord
Pittsburg) and analyzed for mutagenic activity in the Ames test for PAH oxyanions
(N0 - so =) pollutant gases (CO NO N02
o3
so ) and elemental source tracers3 4 2
(including Pb Br Ni Fe and K) Diurnal geographic and seasonal comparisons
were made Statistical techniques including principal component (factor) analysis
were used to explore relationships between aerosol mutagens PAH and source tracers
The results confirmed earlier observations and provided some new insights into the
sources of aerosol mutagens
(i) Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
-iii-
a In this present and previous Contra Costa studies mutagenic density
and PAH were significantly positively correlated with fine fraction
( lt 25 micromd ) Pb andor Br both derived primarily from motor a
vehicles
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions as well as other combustion source particulate matter
c Studies of upwind-downwind freeway data in Los Angeles by Stateshy
wide Air Pollution Research Center (SAPRC) s~ientists have demonshy
strated an incremental burden of direct mutagens in aerosol attrishy
butable to freeway traffic The amount was comparable to the
area wide background mutagen density
(ii) Many results suggest that some mutagens behave as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is supported by the following evidence
a During pollutation episodes in Contra Costa County mutagens were
positively correlated with N03- assumed to be a secondary aerosol
tracer The association of mutagenicity with N0 occurred areashy3
-
wide
3b SAPRC scientists observed that ratios of mutagen densities (revm )
to CO were generally higher at Riverside California a downwind
receptor site than at El Monte an intermediate receptor site in
the Los Angeles basin Since CO is an unreactive combustion
emission the mutagen densityCO ratio takes into account variations
in emissions and atmospheric dispersion Higher ratios at Riverside
suggest atmospheric mutagen formation during aerosol transport
from Los Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study were highest
-iv-
during summer episodes when the prevailing atmospheric conditions
(ie hot dry stagnant) favored chemical transformations Since
Pb like CO is an unreacti ve emission the mutagenic densityPb
ratio should take into account variations in automotive emission
profiles and dispersion Thus the high ratios during episodes in
August 1981 and September 1983 may reflect atmospheric mutagen
formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH mutagens Mutagenicity of some nitro-PAHs exceed the
mutagenicity of the parent PAH by several orders of magnitude in
laboratory analysis Some of these highly mutagenic ni tro-PAHs are
known to be primary pollutants emitted by various combustion
sources However chamber studies have also shown that irradiation
of mixtures of atmospheric hydrocarbons nitric acid (HNO ) and3 reactive gases (NO2 o ) can lead to mutagen formation Thus3 some hydrocarbons may be converted to secondary mutagenic
products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likely
presence of nitroarene mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes and derivatives which are
not only ubiquitious primary pollutants but may also be derived
from secondary atmospheric transformations We infer that such
compounds were probably major contributors to the mutagenicity
of Contra Costa aerosols from the fact that mutagenic activities
of aerosol extracts were two to three times lower in a Salmonella
strain (T A98NR) deficient in an enzyme required for some monoshy
ni troarene activation than in the standard tester strain (T A98)
-v-
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
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11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
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39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
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48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
a In this present and previous Contra Costa studies mutagenic density
and PAH were significantly positively correlated with fine fraction
( lt 25 micromd ) Pb andor Br both derived primarily from motor a
vehicles
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions as well as other combustion source particulate matter
c Studies of upwind-downwind freeway data in Los Angeles by Stateshy
wide Air Pollution Research Center (SAPRC) s~ientists have demonshy
strated an incremental burden of direct mutagens in aerosol attrishy
butable to freeway traffic The amount was comparable to the
area wide background mutagen density
(ii) Many results suggest that some mutagens behave as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is supported by the following evidence
a During pollutation episodes in Contra Costa County mutagens were
positively correlated with N03- assumed to be a secondary aerosol
tracer The association of mutagenicity with N0 occurred areashy3
-
wide
3b SAPRC scientists observed that ratios of mutagen densities (revm )
to CO were generally higher at Riverside California a downwind
receptor site than at El Monte an intermediate receptor site in
the Los Angeles basin Since CO is an unreactive combustion
emission the mutagen densityCO ratio takes into account variations
in emissions and atmospheric dispersion Higher ratios at Riverside
suggest atmospheric mutagen formation during aerosol transport
from Los Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study were highest
-iv-
during summer episodes when the prevailing atmospheric conditions
(ie hot dry stagnant) favored chemical transformations Since
Pb like CO is an unreacti ve emission the mutagenic densityPb
ratio should take into account variations in automotive emission
profiles and dispersion Thus the high ratios during episodes in
August 1981 and September 1983 may reflect atmospheric mutagen
formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH mutagens Mutagenicity of some nitro-PAHs exceed the
mutagenicity of the parent PAH by several orders of magnitude in
laboratory analysis Some of these highly mutagenic ni tro-PAHs are
known to be primary pollutants emitted by various combustion
sources However chamber studies have also shown that irradiation
of mixtures of atmospheric hydrocarbons nitric acid (HNO ) and3 reactive gases (NO2 o ) can lead to mutagen formation Thus3 some hydrocarbons may be converted to secondary mutagenic
products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likely
presence of nitroarene mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes and derivatives which are
not only ubiquitious primary pollutants but may also be derived
from secondary atmospheric transformations We infer that such
compounds were probably major contributors to the mutagenicity
of Contra Costa aerosols from the fact that mutagenic activities
of aerosol extracts were two to three times lower in a Salmonella
strain (T A98NR) deficient in an enzyme required for some monoshy
ni troarene activation than in the standard tester strain (T A98)
-v-
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
-56-
11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
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39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
-60-
48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
during summer episodes when the prevailing atmospheric conditions
(ie hot dry stagnant) favored chemical transformations Since
Pb like CO is an unreacti ve emission the mutagenic densityPb
ratio should take into account variations in automotive emission
profiles and dispersion Thus the high ratios during episodes in
August 1981 and September 1983 may reflect atmospheric mutagen
formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH mutagens Mutagenicity of some nitro-PAHs exceed the
mutagenicity of the parent PAH by several orders of magnitude in
laboratory analysis Some of these highly mutagenic ni tro-PAHs are
known to be primary pollutants emitted by various combustion
sources However chamber studies have also shown that irradiation
of mixtures of atmospheric hydrocarbons nitric acid (HNO ) and3 reactive gases (NO2 o ) can lead to mutagen formation Thus3 some hydrocarbons may be converted to secondary mutagenic
products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likely
presence of nitroarene mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes and derivatives which are
not only ubiquitious primary pollutants but may also be derived
from secondary atmospheric transformations We infer that such
compounds were probably major contributors to the mutagenicity
of Contra Costa aerosols from the fact that mutagenic activities
of aerosol extracts were two to three times lower in a Salmonella
strain (T A98NR) deficient in an enzyme required for some monoshy
ni troarene activation than in the standard tester strain (T A98)
-v-
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
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11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
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39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
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48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
NO3- and the demonstration that mutagenic organic compounds
can be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere The association between mutagens and No3can be
influenced by HNO artifacts produced by sampling on glass fiber3
filters There are two concerns Gas phase HNO can bind to3
glass fiber and artificially increase apparent particulate NO conshy3
centrations More importantly gas phase HNO may catalyze3
chemical tranformations of PAH to produce highly mutagenic nitroshy
aromatic compounds during sample collection on glass fiber The
significance of these potential artifacts cannot be assessed
accurately at present
(iii) For the first time in Contra Costa County industrial contributions to
mutagenic aerosols were suggested by significant positive correlations
between mutagenic density and S (both fine fraction S and so ) at2
Richmond and Martinez Sulfur oxides are major air pollutants in the
vicinity of large oil refineries and chemical plants in Contra Costa County
The major industrial sources of so are refineries in Richmond (Chevron)2
Martinez (Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo
(Union)
bull Routine collection and analysis of 4 month seasonal composite filter samples was
carried out in Contra Costa County between 1979-1984 The three periods were
Nov-Feb March-June and July-Oct These periods approximate the three meteoroshy
logical seasons in the area
This monitoring effort demonstrated that levels of most aerosol pollutants including
mutagens and PAH were highest in the winter (Nov-Feb)
A prime goal of the monitoring was to detect any time trends which may have
occurred Monitoring did indeed reveal a positive trend in the concentration of
mutagenic aerosols despite decreasing or constant levels of the other pollutants
-vi-
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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l Tokiwa H Takeyoshi H Morita K Takahashi K Saruta N Ohnishi Y (1976)
Detection of mutagenic activity in urban air pollutants Mutation Res 38
351-359
2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
typhimurium J Nat Cancer Inst 58 449-451
3 Pitts J Grosjean D Mischke T Simmon V Poole D (1977) Mutagencic activity
of airborne particulate organic pollutants Toxicology Letters l 65-70
4 rv111ller M and Alfheim I (1980) Mutagencity and PAH-analysis of airborne
particulate matter Atmos Environ 14 83-88
5 Chrisp CE Fisher GL (1980) Mutagenicity of airborne particles Mutation
Res 76143-164
6 Wesolowski J Flessel P Twiss S Cheng J Chan R Garcia L Ondo J Fong A
and Lum S (1981) The chemical and biochemcial characterization of particulate
matter as part of an epidemiological cancer study J Aerosol Sci 12 208-212
7 Council on Environmental Quality (CEQ) (1980) Eleventh annual report of the
Council on Environmental Quality Washington DC US Government Printing
Office
8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
Committee of biological effects of atmospheric pollutants Washington DC
10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
carcinogenic compounds isolated from particles in city air Int J Cancer
12233-232
-56-
11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
aromatic hydrocarbons (Nitro-PAH) from diesel engines (1983) JAPCA 33751-
755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
-59-
39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
-60-
48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488
3measured The annual average increased from 5 revertantsm in 1979-80 to 19
revertantsm 3 in 1983-84 A three to four-fold increase in mutagenic density (from 3 38 revertantsm to 27 revertantsm ) was observed over the five winter seasons
Values in the spring increased from 2 to 18 revertantsm 3 while summertime values 3increased by more than a factor of two from 5 to 13 revertantsm Further
monitoring is needed to determine the persistence of these trends
-vii-
TABLE OF CONTENTS
Abstract iii
Ac know ledge ments xii
List of Figures xiii
List of Tables xvii
CHAPTER I PROJECT SUMMARY 1
A Introduction and Statement of the Problem 1
B Project Objectives 2
C Experimental Approach 3
D Summary of Findings 5
E Recommendations for Future Research 9
-viii-
CHAPTER II APPLICATION OF A SALMONELLA MICROSUSPENSION
PROCEDURE TO THE MEASUREMENT OF MUTAGENIshy
CITY IN AIR PARTICULATE MATTER HIGH RESOshy
LUTION DIURNAL VARIATIONS 11
A Summary 11
B Introduction 12
C Materials and Methods 13
D Results and Discussion 16
E Conclusions 21
CHAPTER III SOURCES OF MUTA GENS AND POLYCYCLIC AROMA TIC
HYDROCARBONS (PAH) IN CONTRA COSTA COMMUNITY
AEROSOLS DURING POLLUTION EPISODES DIURNAL
GEOGRAPHIC AND EPISODE VARIATIONS 22
A Introduction 22
B Experimental Methods 22
C Results and Discussion 26
-ix-
26
CHAPTER IV
REFERENCES
l Meteorological Conditions During Episodes
2 Combined Episode Data with Diurnal Comparisons 28
3 Geographic Differences 38
4 Episode Comparisons 41
0 Conclusions 44
SEASONAL VARIATIONS AND TRENDS IN THE
CONCENTRATIONS OF MUTA GENS AND PAH IN
CONTRA COST A COUNTY COMMUNITY AIR 46
A Introduction 46
B Experimental Methods 46
C Results and Discussion 48
0 Conclusions 54
56
-x-
62 APPENDICES
APPENDIX I Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling
Episodes (1982-1984)
APPENDIX II San Francisco Bay Area Weather Factors During Six
Sampling Episodes (1982-1984)
APPENDIX III Complete Correlation Matrices for Combined Episodes
Daytime and Nighttime Samples and the Four Stations
APPENDIX IV Complete Data Set for Contra Costa Seasonal
Composites Nov 1979-0ct 1984
APPENDIX V Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-xi-
ACKNOWLEDGMENTS
Once more the authors gratefully acknowledge the continuing collaboration of J
Sandberg D Levaggi W Siu H Chew R England A Fredenberg N Balberan and
their colleagues of the Bay Area Air Quality Management District (BAAQMD) who
furnished sampling sites skillfully provided forecasts and collected many of the air
samples Thanks again to R Brown and the Mountain View Sanitary District Martinez
for hospitality in providing a sampling site
We wish to express our appreciation to the following staff of the Air and Industrial
Hygiene Laboratory who provided consultation and performed chemical determinations
S Twiss W Wehrmeister A Cartano Z Ilejay F Boo N Fansah E Jeung E
Hoff er and A Alcocer We also thank R Giaque of the Lawrence Berkeley Laboratory
LBL who performed the trace element analysis and J Jaklevic and B Loo (LBL) who
provided the Automatic Dichomotous Samplers
Finally we thank Project Officer C Unger for his direction and encouragement
This report was submitted in fulfillment of Interagency Agreement No Al-162-32
Carcinogens and Mutagens in Ambient Particulate Matter by the California Department
of Health Services under the sponsorship of the California Air Resources Board Work
was completed as of May 31 1985
-xii-
LIST OF FIGURES
I-1 Structure and Nomenclature of 10 POMs la
I-2 Locations of Sampling
County California
Stations in Contra Costa
3d
I-3 Logistical Plan for Analysis of Hi-Volume Air
Filters Collected in Contra Costa County for
Seasonal Composites 4a
II-1 Dose-response curves for composite hi-vol air
particle extract Determined using the plate
incorporation test and microsuspension procedure
with (a) and without (b) rat liver 59 17b
II-2 Diurnal variations of mutagenicity of fine airborne
particles collected in Rodeo California and
measured in the microsuspension assay 18a
Il-3 Diurnal Variation of Mutagenicity of fine airborne
particles collected in Berkeley and measured in
the microsuspension assay with (a) and without
(b) addition of rat liver 59 19a
II-4 Diurnal variation of mutagenicity of fine airshy
borne particles collected in Martinez California
and measured in the microsuspension assay TA98
with 59 (a) T A98 without 59 (b) T A98NR withshy
out 59 (c) 19b
Il-5 Correlation of airborne lead and mutagenicity
measured in the microsuspension assay from fine
particles collected at Martinez California r = 092 20b
-xiii-
IV-1 Lead Seasonal Composites Average of Three Stations
Lead concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50a
IV-2 Nitrate Seasonal Composites Average of Three Stations
Nitrate concentrations were measured every sixth day at
each of three stations and the results average over four
month seasons (July-October November-February
March-June) 50b
IV-3 TSP Mass Seasonal Composites Average of Three Stations
Total suspended particulate mass concentrations were
measured every sixth day at each of three stations and the
results averaged over four month seasons (July-October
November-February March-June) 50c
IV-4 Sulfate Seasonal Composites Average of Three Stations
Sulfate concentrations were measured every sixth day at
each of three stations and the results averaged over four
month seasons (July-October November-February
March-June) 50d
IV-5 Organics Seasonal Composites Average of Three Stations
Benzene soluble organic concentrations were measured every
sixth day at each of three stations and the results averaged
over four month seasons (July-October November-February
March-June) 50e
IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
Stations BAP concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50f
-xiv-
IV-7 Coronene Seasonal Composites Average of Three Stations
Coronene concentrations were measured in seasonal composite
extracts prepared from hi-vol filters collected every sixth day
at three stations Separate station composites were prepared by
combining pieces of filters every four months and extracting
Composite values at the three stations were averaged
to obtain the seasonal composite 50g
IV-8 Benzanthrone Seasonal Composites Average of Three
Stations Benzanthrone concentrations were measured in
seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stations were averaged to obtain the seasonal composite 50h
IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average
of Three Stations Mutagenic densities (-59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters
every four months and extracting Composite values at the
three stations were averaged to obtain the seasonal composite 50i
IV-10 Mutagenic Density (Ta98+59) Seasonal Composites Average
of Three Stations Mutagenic densities (+59) were measured
in seasonal composite extracts prepared from hi-vol filters
collected every sixth day at three stations Separate station
composites were prepared by combining pieces of filters every
four months and extracting Composite values at the three
stati ans were average to obtain the seasonal composite 50j
IV-11 Mutagenic Density Trends for Nov-Feb Average of
Three Stations Trends in mutagenic density for the five
winter seasons 1979-1984 are compared by linear regression
analyses For TA98+S9 r=085 and b(slope)= 40 revyr
For TA98-S9 r=079 and b=l9 revyr 50k
-xv-
IV-12 Mutagenic Density Trends for March-June Average of
Three Stations Trends in mutagenic density for the five
spring seasons 1979-1984 are compared by linear regression
analysis For TA98+S9 r= 095 and b(slope) = 39 revyro
For TA98-S9 r=091 and b = 19 revyr 501
IV-13 Mutagenic Density Trends for July-Oct Average
of Three Stations Trends in mutagenic density for the
five summer seasons 1979-1984 are compared by linear
regression analysis For TA98+S9 r=083 and b(slope)=
20 revyr For TA98-S9 r=095 and b=ll revyr 50m
IV-14 Seasonal Composite Trends for TA98NRTA98 Average
of Three Stations Five year trends in the mutagenic
density ratio TA98NR(-S9)TA98(-S9) are compared by season 50n
-xvi-
LIST OF TABLES
I-1 Acronyms for Air Pollutant Variables used in the
Analysis and Interpretation of Contra Costa Data 3a
1-2 Methods used for Collection and Analysis of
Particulate and Gaseous Air Pollutants 3b
I-3 Sampling and Analytical Plan for Mutagen Source
Identification 3c
II-1 Comparative Mutagenic Activity of Mutagens in the
Plate Incorporation and Microsuspension Procedures 16a
II-2 Comparison of Direct Mutagenic Activity of 2-Nitroshy
fluorene 4-Nitroquinoline-N-oxide and Composite
Berkeley Air Filter Extract in T A98 and T A98NR
as determined by the Microsuspension Procedure 17a
Il-3 Mutagenicity of Particles Collected by Hi-Volume
and Dichotomous Air Samplers run in parallel at
Martinez California 20a
III-1 Summary Statistics for Air Pollutants from
Episodes Combined Data 1982middot1984
Six
29a
lll-2 Summary Statistics for Air Pollutants from
Episodes Combined Data 1981-1982
Three
29b
lll-3 Summary Statistics for Air Pollutants from
Episodes Daytime Samples 1982-1984
Six
32a
III-4 Summary Statistics for Air Pollutants from
Episodes Nighttime Samples 1982-1984
Six
32b
-xvii-
III-5 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Combined
Episode Data 1982-1984 32c
IIl-6 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Daytime
Samples 1982-1984 32d
III-7 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants Nighttime
Samples 1982-1984 32e
III-8 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data 1982-1984 (N = 71) 33a
III-9 Principal Component Factors for Particulate Air
Pollutants Daytime Samples 1982-1984 (N = 27) 33b
III-10 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples 1982-1984 (N = 44) 33c
III-11 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Mutagenic Density (+S9) 34a
III-12 Principal Component Factors for Particulate Air
Pollutants Daytime Samples Including Mutagenic
Density (+S9) 34b
III-13 Principal Component Factors for Particulate Air
Pollutants Nighttime Samples Including Mutagenic
Density (+S9) 34c
-xviii-
III-14 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including Coronene 36a
III-15 Principal Component Factors for Particulate Air
Pollutants Combined Episode Data Including
Benzanthrone 36b
III-16 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Richmond
38a
III-17 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Martinez
38b
III-18 Summary Statistics for Air Pollutants from
during Six Episodes 1982-1984
Concord
38c
III-19 Summary Statistics for Air Pollutants from Pittsburg
during Six Episodes 1982-1984 38d
III-20 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Richmond 40a
IIT-21 Correlations between Mutagenic Density (revm 3)
Selected PAH and Air Pollutants during Episodes
at Martinez 40b
III-22 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Concord 40c
-xix-
III-23 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants during Episodes
at Pittsburg 40d
III-24 Summary Statistics for Air Pollutants from Episode I 41a
III-25 Summary Statistics for Air Pollutants from Episode II 41b
III-26 Summary Statistics for Air Pollutants from Episode III 41c
III-27 Summary Statistics for Air Pollutants from Episode IV 41d
III-28 Summary Statistics for Air Pollutants from Episode V 4le
IIl-29 Summary Statistics for Air Pollutants from Episode VI 4lf
III-30 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode I 43a
III-31 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode II 43b
Ill-32 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode III 43c
III-33 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode IV 43d
Ill-34 3Correlations between Mutagenic Density (revm )
Selected PAH and Air Pollutants from Episode V 43e
III-35 Correlations between Mutagenic Density (revm3)
Selected PAH and Air Pollutants from Episode VI 43f
-xx-
IV-1 Mean Concentrations of Air Pollutants Sampled
three Contra Costa Stations November 1979-
June 1984
at
48a
IV-2 Seasonal Variations in Contra Costa Air Pollutant
Concentrations (Three Station Averages) November
1979-June 1984 48b
IV-3 Composite Mutagenicity Trend
Data Stratified by Location 500
IV-4 Composite Mutagenicity Data Stratified
by Season and Location 50p
IV-5 Linear Regression Analysis of Composite
Mutagenicity Data (Mutagenicity Density
in TA98 +S9) Year versus
Location and Season 50q
-xxi-
D-IAPTER I
PROJECT SUMMARY
A Introduction and Statement of the Problem
A variety of chemical mutagens and carcinogens are known to be present in
particulate matter in urban community air (1-9) Recent epidemiological conshy
clusions place the number Cgtf cancer deaths in the US due to environmental
pollution (air water and soil) at 8000 annually (7) It has been estimated that
outdoor community air pollution alone may be the cause of about 15 of the
present lung cancer cases among non-smoking residents in Contra Costa
County (8) neglecting contributions from indoor air pollution Thus it may be
argued that exposure to mutagens and carcinogens in outdoor community air
remains a significant public health concern which warrants continued monitoring
and investigation
Carcinogenic chemicals found in air particulate matter include certain polycyclic
aromatic hydrocarbons (PAH) such as benzo(a)pyrene (BaP) and benzo(k)fluoranshy
thene (9) Structures of these and other PAH are shown in Figure I-1 However
these chemicals constitute only a small fraction of the total carcinogenic
potential Organic extracts of ambient particulate organic matter (POM) are
significantly more carcinogenic and mutagenic than expected on the basis of the
amounts of the measured chemicals present (1011) The excess mutagenicity
as defined by the Ames test (12) reflects a significant gap in our knowledge
The gap may be due to our inability until recently to measure small concentrations
of carcinogenic and highly mutagenic nitroarenes (eg 1-nitropyrene) (13) which
are present in diesel exhaust particulates (14) and urban air (151617) These
compounds probably account for a significant portion of the observed mutagenicity
of urban air particulate matter
However the measurement of mutagenicity in a given geographical area and
even the chemical identification of the mutagens present are of limited public
health value unless the major sources of mutagenicity can be identified and
controlled With few exceptions the sources of mutagens and carcinogens in
air particulates are unknown In Contra Costa County for example PAH
-1-
Chrysene Benz(a)anthracene Benzo(e)pyrene
Benzo(b)fluoranthene Benzo(a)pyrene Benzo (k )fluoranthene
Dibenz(ah )anthracene Benzo(ghi)perylene Coronene
~ 0
7-H-benz(de)anthracen-7-one
FIGURE I-1 STRUCTURE AND NOMENCLATURE OF 10 POMs
-la-
appeared to be derived principally from vehicular emissions but these compounds
account for less than ten percent of measured mutagenicity (6) Until recently
the principal sources of mutagens remained obscure
Concern about sources of mutagen led to a previous study of mutagens in Contra
Costa County carried out by the Air and Industrial Hygiene Laboratory (AIHL)
under contract to the California Air Resources Board (CARS) (18) The AIHLshy
CARB project provided the background to the present investigation The previous
study measured the mutagenic activity of ambient aerosol extracts and quantishy
tated a number of organic compounds which contribute to the mutagenicity
Air sampling was carried out during three seasonal pollution episodes in 1981-1982
Solvent extracts of POM were analyzed for mutagenic activity in the Ames
Salmonella test and for polycyclic aromatic hydrocarbons (PAH) by high pressure
liquid chromatography (HPLC) with fluorescence detection Pb Ni Fe N03-
so = o3 CO NO N02 and were also measured Diurnal variations in4 so2 mutagenicity and chemical pollutant concentrations were compared Mutagenicity
was found to be consistently and strongly associated with lead-containing fine
particles (lt 25 micro md ) emitted primarily by gasoline powered vehicles without a
catalysts During a winter inversion possible contributions to PAH from
residential wood combustion were also noted
The previous study also revealed positive correlations between mutagenicity and
nitrates during a summer pollution episode We speculated earlier that this
correlation could reflect chemical formation of nitro PAH compounds in the
atmosphere and suggested that in some respects the formation of mutagenic
aerosols was similar to the formation of photochemical oxidant the effects of
atmospheric dispersion and transformation both need to be considered Since
this suggestion could have policy implications for control of oxides of nitrogen
further investigation was required
B Project Objectives
The present study was designed to followup these earlier leads by addressing
three topics which are critical to a further understanding of mutagens and
carcinogens in community air 1) the validation of a more sensitive method
-2-
for measuring aerosol mutagens 2) the identification of the sources and the
possible routes of atmospheric chemical formation of aerosol mutagens and 3)
the investigation of seasonal variations and the recent trends in airborne mutagen
and PAH concentrations in Contra Costa County between 1979 and 1984
C Experimental Approach
The research carried out under this and the previous CARS-contract (18)
employed a similar experimental approach and methods The abbreviations of
air pollutants and methods used for their collection and analysis are listed in
Tables I-1 and 2
l Application of the Salmonella Microsuspension Procedure to the Measureshy
ment of Mutagenicity in Air Particulate Matter
A simple and highly sensitive version of the Salmonella liquid incubation
assay (19) was validated using pure chemical mutagens and then applied
to the measurement of air particulate mutagenicity These applications
included diurnal studies carried out at several locations In one experiment
selected criteria pollutants (Pb N02 03 so ) were sampled concurrently2 to provide information about sources of mutagens
2 Intensive Sampling for Mutagen and PAH Source Identification
A second focus of the present effort was on source identification Six
pollution periods were sampled intensively to investigate sources of mutashy
gens and PAH The sampling and analytical plan for source identification
is shown in Table I-3 Separate day (0600-1800) and night (1800-0600)
sampling was carried out over 36 hour episodes Episodes were stable
meteorological periods when concentrations of pollutants were relatively
high Samples were collected at four locations (Richmond Martinez
Concord and Pittsburg) in the northern industrialized portion of Contra
Costa County (Figure I-2) The northern section of the county contains
heavy industry including five major petroleum refineries and many chemical
-3-
TABLE 1-1
ACRONYMS FOR AIR POLLUTANT VARIABLES USED IN THE ANALYSIS AND INTERPRETATION OF CONTRA COSTA DATA
TSP
so= 4
NO -3
ORG
BAP
BKF
BGP
COR
BZO
PBF
BRF
FEF
SIF
KF
ZNF
SF
CLF
M39BPS9
M398MS9
M398NRM
NR98M3
ORG98PS9
ORG98MS9
03 co NO
N02
so2
Total Suspended Particulate Mass
Sulfate Mass
Nitrate Mass
Benzene Soluble Organics
Benzo(a)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Benzanthrone (all isomers)
Fine fraction Lead
Fine fraction Bromine
Fine fraction Iron
Fine fraction Silica
Fine fraction Potassium
Fine fraction Zinc
Fine fraction Sulfur
Fine fraction Chlorine
Revertants per m3 in TA98+S9
Revertants per m3 in TA98-S9 3Revertants per m in TA98NR-S9 3Revertants per m in TA98NRTA98
Revertants per ORG in TA98 + S9
Revertants per ORG in TA89-S9
Ozone
Carbon Monoxide
Nitrogen oxide
Nitrogen dioxide
Sulfur dioxide
3microgm 3microgm 3microgm 3microgm
3ngm
3ngm
3ngm 3ngm 3ngm 3
ngm 3
ngm 3
ngm 3ngm 3ngm 3ngm 3ngm 3ngm 3revm 3revm 3revm
revmicrog
rev microg
pphm
ppm
pphm
pphm
pphm
-3a-
TABLE 1-2
METHODS USED FOR COLLECTION AND ANALYSIS OF PARTICULATE
AND GASEOUS AIR POLLUTANTS
Pollutant Collection (Medium) Analysis
TSP
so -4
N03
ORG
PAH
Mutagens
Trace elements
so2
Pb only
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glass fiber)
Hi-vol (glassmiddot fiber)
Dichotomous (Teflon)
Dichotomous (Teflon)
Hi-Vol (glass fiber)
Dasibi Model 1003-AH
Thermal-electron Model 140
Bendix Model 8301-SCA
Thermal-electron Model 43
Gravimetric
Turbidimetric
Colorimetric
Benzene extraction
HPLC - fluorescence
Standard Ames test
Microsuspension Ames test
X-ray fluorescence
II ii
Ultraviolet absorption
Chemiluminescence
Infrared absorption
Fluorescence
-3b-
TABLE 1-3
SAMPLING AND ANALYTICAL PLAN FOR MUTAGEN SOURCE IDENTIFICATION
Day-Night Collection 6 am -6 pm -
Collect Particulates on
Hi-vol 1 (glass fiber)
Mass Sulfate Nitrate Lead Organics
Hi-vol 2 (glass fiber) Refrigerate immediately
Mutagenicity PAH
Dichotomous Samplers
Agency Performing
Analysis
AIHL AIHL AIHL AIHL Ailll
AIHL AIHL
DHS-LBL
BAAQMD
BAAQMD
BAAQMD
BAAQMD
BAAQMD
(membrane or Teflon filter)
Multielemental analysis
Collect Gas Data
NO X
co
Collect Meteorological Data
Wind direction Wind speed
6 pm 6 am
Analytical Method
Gravimetric Turbidimetric Colorimetric X-ray Fluorescence Benzene Extraction
Ames HPLC
Energy Dispersive X-ray Fluorescence
Chemiluminescence Photoshymetry
Non-Dispersive Infrashyred Absorption
Fluorescence Photometry
Ultraviolet Absoprtion
-3c-
~ (~ SAN PABLOIi BAY
LOCATIONS OF SAMPLING STATIONS
IN CONTRA COSTA COUNTY CALIFORNIA
FIGURE I-2
-3d-
plants Three of the stations (Richmond Concord Pittsburg) are part of
the Bay Area Air Quality Management District (BAAQMD) network
Martinez was a temporary site adjacent to a petrochemical refinery
Each location had samplers to collect air particulate matter for analysis
of mutagenicity PAH trace metals (including Pb Ni K Si) N0 - SO = 3 4
and total mass Gaseous pollutants (CO so2
NO N02 o ) were also3 measured At Martinez wind speed and direction were obtained Chemical
and mutagenicity data were combined using simple and complex statistical
methods in an attempt to identify sources of mutagens and selected PAH
3 Collection and Analysis of Seasonal Composites
To determine seasonal variations and trends samples were collected at
the same three permanent stations of the BAAQMD network (Concord
Pittsburg and Richmond) used for intensive sampling Hi-vol filter samples
were collected every sixth day at each station for routine monitoring
purposes and were analyzed for total suspended particulate (TSP) SO =4
N0 - organics and Pb~ A portion of each filter was composited for PAH3
and mutagenicity testing Each station was composited separately The
logistical plan for analysis of hi-vol filters collected for seasonal composhy
sites is shown in Figure I-3 Filters from each of the three stations were
composited over four-month intervals (July-October November-February
March-June) to give composite samples for analysis These periods
approximate the three meteorological seasons in the San Francisco Bay
air basin and also correspond with those used in our previous studies in
Contra Costa County (18)
Samples collected during the period July 1982-0ctober 1984 were composhy
sited and analyzed for PAH and mutagenic activity When combined with
results of previous studies these provide a continuous data base of the
concentrations of specific PAH and mutagenic activity in Contra Costa
air particulate material collected over five years since November 1979
Results of PAH and mutagenicity measurements in composite samples
were also compared with TSP N0 - so = Pb and total organics on a3 4
season-by-season basis
-4-
I + PJ I
FIGURE I-3 Logistical Plan for Ana1ysis of Hi-Volume Air Filters Col1ected in Contra Costa County for Seasonal Composites
Analyzed for N03 Colorimetrically
SO4 Turbidimetrically (BAAOMD) Analyzed for PAHs
by GC-MS HPLC
(AIHL)
Analyzed for Pb by
X-ray fluorescence (AIHL)
To BAAOMD
i ----
FILTERS 1 Collected 2 Weighed 3 Delivered to AIHL
(BAAOMD)
FILTERS
1 Logged in 2 Deposit area measured 3 Cut and distributed for analysis
(AIHL)
Ar------ -----
Igt
_J_
frac14dt ~--
I
(Supple t ment)
Analyzed for MUTAGENIC ACTIVITY
in the Ames Assay (AIHL)
middot
bull
bullbull
TSP Gravimetrically
(BAAOMD)
~
I
__ Analyzed for BSO by soxhlet extraction
(AIHL)
DATA BANK (AIHL)
1 Results recorded 2 Data key punched and entered
into computer 3 Cumulative results printed out
each 4 months
D Summary of Findings
Efforts to validate and apply a highly sensitive version of the Ames test to air
samples (Chapter II) yielded the following findings
l The 10 fold increased sensitivity of the microsuspension Ames test made
possible high resolution diurnal studies of mutagenicity in small samples
of only 2 hours duration
2 Diurnal variations in mutagenic density (rev m 3) of more than a factor
of 10 were observed
3 Diurnal variations in mutagenic density were highly correlated with fine
fraction Pb in a pilot field study
4 The test can be applied in future studies where sample mass is a limiting
factor
Intensive episode sampling and analysis for source identification (Chapter III)
confirmed earlier observations and provided now new insights into sources of
aerosol mutagens
1 Several lines of evidence indicate that some mutagenic aerosols are primary
automotive pollutants emitted directly into the atmosphere
a In this and earlier Contra Costa studies mutagens (and PAH) were
significantly correlated with fine fraction Pb and Br indicating
contributions from primary automotive emissions
b Chemical analysis by other investigators has identified mutagens
(various PAH and nitroarenes) in on-road vehicle particulate
emissions (20) as well as other combustion source particulate matter
(21)
-5-
c Studies of upwind-downwind freeway data in Los Angeles by
Sweetman et al (22) have demonstrated an incremental burden of
direct mutagens in aerosol attributable to freeway traffic which
was comparable to the area wide background mutagen density
2 Many results suggest that some mutagens behaved as secondary aerosols
The hypothesis that some mutagenic aerosols are formed in the atmosphere
is strengthened by the following evidence
a During pollution episodes in Contra Costa County mutagens were
positively correlated with NO-3 assumed to be a secondary aerosol
tracer The association of mutagenicity with NO3 occurred areashy
wide
b Pitts and co-workers (23) observed that ratios of mutagen densities
(rev m3) to CO were generally higher at Riverside a receptor site
than at El Monte an intermediate receptor location in the Los
Angeles basin Since CO is an unreactive combustion emission the
mutagen densityCO ratio takes into account variations in emissions
and atmospheric dispersion Higher ratios at Riverside suggest
atmospheric mutagen formation during aerosol transport from Los
Angeles
c The ratios of mutagenic densities to Pb which we have measured
in Contra Costa County in this and a previous study (18) were
highest during summer episodes when the prevailing atmospheric
conditions (ie hot dry stagnant) favored chemical transformations
Since Pb like CO is an unreactive emission the mutagenic
density Pb ratio should also take into account variations in (autoshy
motive) emission profiles and dispersion Thus the high ratios during
episodes in August 1981 (18) and September 1983 (shown below)
may reflect atmospheric mutagen formation
d Smog chamber studies have demonstrated the formation of nitroshy
PAH and other mutagens Mutagenicity of some nitro-PAHs exceed
-6-
the mutagenicity of the parent PAH by several orders of magnitude
in laboratory analysis Some of these highly mutagenic nitro-PAH
are known to be primary pollutants emitted by various combustion
sources However chamber studies (2425) have also shown that
irradiation of mixtures of atmospheric hydrocarbons nitric acid
(HNO ) and reactive gases (NO2
o ) can lead to mutagen formation3 3 Thus some some hydrocarbons may be converted to secondary
mutagenic products under simulated atmospheric conditions
e Measurements in a nitroreductase mutant indicate the likeley preshy
sence of nitroorganic mutagens Less than 10 of the total
mutagenicity in ambient air samples is due to identified PAH Thus
most of the mutagenicity remains to be explained in chemical
terms A substantial proportion of this excess mutagenicity may
be due to highly mutagenic nitroarenes which are not only ubiquishy
tious primary pollutants but may also be derived from secondary
atmospheric transformations We infer that nitroarenes were
probably major contributors to the mutagenicity of Contra Costa
aerosols from the fact that mutagenic activities of aerosol extracts
were two to three times lower in a Salmonella strain (T A98NR)
deficient in an enzyme for some mononitroarene activation than
in the standard tester strain (TA98) With respect to mutagenicity
of community air collected in other cities this finding is not unique
For example air particulate samples from Los Angeles (23) and
Detroit (26) also showed markedly reduced mutagenic activities in
nitroreductase deficient strains
f Finally measurement artifacts confound the secondary mutagen
hypothesis The positive correlations of mutagenic density with
N3 - and the demonstration that mutagenic organic compounds can
be formed under simulated atmospheric conditions support the
hypothesis of secondary formation of mutagenic aerosols in the
atmosphere However interpretation is complicated by measurement
artifacts in nitrates and nitro-aromatic compounds The association
between mutagens and NO could be influenced by HNO artifacts3 3
-7-
produced by sampling on glass fiber filters There are two concerns
Gas phase HNO can bind to glass fiber and artificially increase3 apparent particulate NO concentrations (27) More importantly
3 -
gas phase HNO may catalyze chemical transformations of PAH3 to produce highly mutagenic nitroaromatic compounds during sample
collection on glass fiber (13) The significance of these potential
artifacts can not be assessed accurately at present
3 For the first time industrial contributions to mutagenic aerosols were
also suggested by significant positive correlations between mutagenic
density and S (both fine fraction S and so ) at Richmond and Martinez2
These sulfur oxides are major air pollutants in the vicinity of large oil
refineries and chemical plants concentrated in Contra Costa County The
major industrial sources are refineries in Richmond (Chevron) Martinez
(Shell Tosco) and Benicia (Exxon) and a chemical plant in Rodeo (Union)
(28)
Routine collection and analysis of seasonal composite filters in Contra Costa
County between 1979-1984 (Chapter IV) revealed both seasonal variations and
trends
1 Concentrations of mutagens PAH and the standard air pollutants (TSP
Pb NO - so =) were highest during the winter (Nov-Feb) season PAH3 4
exhibited the greatest seasonal changes 3-10 fold High wintertime PAH
concentrations could reflect contributions from residential wood combusshy
tion
2 A positive trend in concentrations of mutagenic aerosols (+S9) was found
between 1979 and 1984 For example a nearly four-fold increase in the 3annual average mutagenic density (+S9) from 5 to 19 revm was observed
over the five years of monitoring
3 The positive trend in mutagenicity was in contrast to the fairly constant
(annual average) levels of PAH and the decreasing levels of the standard
pollutants The decrease in Pb was most apparent For example over
-8-
the five winter seasons (1979-1984) Pb decreased from 057+013 ngm 3
3to 027~003 ngm The Pb gasoline phase-out program in the Bay Area
or different meteorological factors for the sampling seasons may be
responsible
E Recommendations for Future Research
The partial answers derived from the present research effort also generated
additional questions for possible future research
Investigation of sources has lead to the suggestion that mutagens may be formed
atmospherically during normal aging of community aerosols Before endorsing
this suggestion further several measurement questions must be addressed As
noted above the apparent association between mutagens and NO could be3 influenced by HNO artifacts produced by sampling on glass fiber filters Gas
3 phase HNO3 can bind to glass fiber and artificially increase apparent particulate
NO -concentrations Appel and co-workers (27) have recently compared artifact3 NO formation on different filter media Laboratory and atmospheric sampling
3 -
studies were performed to evaluate glass fiber and Teflon filters for their
abilities to form artifact particulate nitrate with HNO bull At nitric acid dosages3
representative of those in the atmosphere glass fiber filters retained gt94 of
the HNO and Teflon lt2 of HNO3
3
Gas phase HNO3
may also catalyze chemical transformations of PAH to produce
highly mutagenic nitroaromatic compounds These transformations can occur
both in the atmosphere and on filters during sample collection Pitts et al (13)
first showed the formation of directly mutagenic nitroderivatives from PAH
coated on glass fiber filters and exposed to flows of air containing NO and2
traces of nitric acid Extending this research Pitts and co-workers (23) have
more recently studied sampling artifacts utilizing two filter types (glass fiber
and Teflon-impregnated glass fiber) The ratios of mutagen densities for POM
simultaneously collected on glass fiber and Teflon-impregnated glass fiber varied
by more than a factor of ten The greatest differences occurred during periods
of elevated o concentrations suggesting that under such conditions there is an3
artifact effect associated with particulate collection (probably) on glass fiber
-9-
filters Ambient concentrations of HNO and other reactive gases (NOx o )3 3 in Contra Costa County are not as high as in El Monte and Riverside where
these artifacts were studied Nevertheless direct evaluation of possible HNO3-
glass fiber effects in Contra Costa air samples should be done Experiments
are recommended to compare mutagenicity and NO values in aerosols collected3 -
on glass-fiber and Teflon-impregnated glass fiber filters in samplers equipped
with or without HNO 3 denuders
A further recommendation concerns industrial emissions We have observed for
the first time in Contra Costa County significant positive correlations between
mutagenicity and the petrochemical tracer S at Richmond and Martinez Petroshy
chemical and other chemical sources may therefore contribute to mutagenic
emissions Follow-up research on stationary source emissions should be done
This research should provide sampling methods for both volatile and aerosol
mutagens at Richmond and Martinez mutagenicity was positively correlated with
gaseous so2 as well as fine S aerosols
A final recommendation is to maintain and expand the monitoring network for
mutagens and PAH in light of the increasing trends in mutagenicity observed
in recent years To verify the trend analysis routine monitoring should continue
in Contra Costa County and be extended to include other high pollution locales
in the Bay Area (eg southern Santa Clara County) and adjacent air basins (eg
Sacramento-San Joaquin Valley Chico to Bakersfield) Existing air sampling
networks would be used Because samples are routinely collected at sites in
these networks and Ames and PAH testing are routinely carried out in AIHL
the cost would be minimal
-10-
CHAPTER II
APPLICATION OF A SALMONELLA MICROSUSPENSION PROCEDURE TO THE
MEASUREMENT OF MUTAGENICITY IN AIR PARTICULATE MATTER
HIGH RESOLUTION DIURNAL VARIATIONS
A Summary
A simple modification of the Salmonella liquid incubation assay (19) was used
to determine mutagenic activity of airborne particulate matter The modification 9consists of adding ten times more bacteria (approximately 10 per incubation
tube) and five to ten times less metabolic enzymes compared to the plate
incorporation method The mixture volume is approximately 02 ml and the
mixture is incubated for 90 minutes before pouring it according to the standard
protocol The modified procedure was approximately 10 times more sensitive
than the standard plate incorporation test for detecting mutagens in air particle
extracts and approximately 13-30 times more sensitive for the chemical mutagens
2-nitrofluorene 4-nitroquinoline-N-oxide 2-aminofluorene and benzo(a)pyrene in
bacterial strain T A98 This microsuspension procedure was applied to air
particulate samples collected with low volume (15-50 liters per min) virtual
dichotomous air samplers Mutagenic activity was detected in particle extracts
obtained from one cubic meter of air or less (17 microg of extract) and was
associated exclusively with fine particles (aerodynamic diameters of less than
25 microm) Diurnal patterns of mutagenic activity (TA98 revertants per cubic
meter air) were investigated by measuring filter extracts from two-hour samples
collected in three San Francisco Bay Area cities during air pollution episodes
Four criteria pollutants - lead nitrogen dioxide ozone and sulfur dioxide were
simultaneously sampled at one location Mutagenicity from fine particles sampled
at this location was highly correlated with lead and much less correlated with
nitrogen dioxide ozone and sulfur dioxide The microsuspension procedure is
applicable in testing samples of limited mass
-11-
B Introduction
Mutagenic activity of solvent extracts from community air particulate matter
has been studied by a number of investigators (l-6) The activity is a rough
index of exposure to potential carcinogens aids in the chemical characterization
and identification of mutagens and helps better define the sources of chemical
mutagens The Salmonella typhimuriummicrosome test (12) has often been used
in air pollution mutagen studies It is the most validated of the short-term
genotoxicity tests and is convenient and economical to use The airborne
particulate matter used in mutagenicity studies are collected by samplers usually
of the hi-vol cascade or electrostatic precipitator type which draw large volumes
of air through filters to provide enough sample mass for subsequent biological
or chemical testing Hi-volume-type samplers have also been combined and
operated simultaneously (29) to acquire several times as much material as a
single hi-vol sampler Limited numbers of certain hi-volume samplers are
available and for some of them such as the ultra high volume sampler (17)
mobile deployment is difficult due to the large size of the instrument Furthershy
more the more volatile mutagens adsorbed onto the particles may be lost or
chemically transformed because such a large volume of air passes over the
particle sample (30)
The problems of sampling can be reduced by the use of more sensitive bioassays
to detect mutagenicity in samples of limited mass The more sensitive assays
would also facilitate subsequent separation and identification of specific
mutagens
We report here progress in using a highly sensitive modification of the Salmonella
liquid incubation assay to measure the mutagenicity of airborne particle extracts
The simple modification was previously described for detecting mutagens in
cigarettes smokers urine (19) with an increase in sensitivity of approximately
20 times that of the plate incorporation test We describe first the relative
sensitivity of the modification to the plate incorporation test using known
mutagens and second the initial application of the modification for measurement
of mutagenic activity in a composite air filter extract and filter extracts taken
from low volume size selective dichotomous samplers
-12-
C Materials and Methods
l Chemicals
Benzo(a) pyrene (BP Gold Label) 2-aminofluorene (2-AF) 2-nitrofluorene
(2-NF) and 4-nitroquinoline-N-oxide (4-NQO) were purchased from Aldrich
Chemical company Milwaukee Wisconsin and were used without further
purification The extraction solvents (methanol dichloromethane and
toluene) were glass-distilled OmniSorb brand purchased from Matheson
Coleman and Bell Gibbstown New Jersey Dimethyl sulfoxide was
Photo-rex grade and was purchased from JT Baker Chemical Company
Phillipsburg New Jersey
2 Criteria Gas Pollutant Sampling and Analysis
At one sampling site (Martinez California) gaseous air pollutants were
simultaneously measured by the Bay Area Air Quality Management District
using a mobile sampling van Ozone was measured by ultraviolet absorption
with a Dasibi model 1003-AH Ozone Monitor Nitrogen dioxide was
measured by chemiluminescence with a Thermal-electron Model 140
analyzer and Sulfur dioxide was measured by fluorescence using a Thermalshy
electron Model 43 pulse-fluorescence analyzer All these methods are
EPA reference methods or have been certified as equivalent (31)
3 Air Particle Collection and Sample Preparation
The plate incorporation and the microsuspension procedures were compared
using a composite filter extract from 24-hour hi-vol samples collected
for 10 consecutive days during the summer of 1982 Particulate samples
were collected on 8 x 10 inch glass-fiber filters (EPA equivalent from
Whatman Ltd Springfield Kent England) The hi-vol sampler had a flow
rate of l m3min and was placed on the roof (approximately 30 meters
above street level) of the Department of Health Services Building
Berkeley California
-13-
Collections of size-segregated fine ( lt25 microm aerodynamic diameter) and
coarse (25-15 micro m aerodynamic diameter) air particulate fractions were
made at Rodeo California during the summer of 1982 and at Berkeley
and Martinez California during the fall of 1982 using dichotomous air
samplers The town of Rodeo is located approximately 10 miles north
of Berkeley A major freeway and chemical plants are nearby At Rodeo
size-segregated samples were collected with a standard Sierra Model
Dichotomous sampler (Sierra Instrument Corp Carmel Valley CA) opershy
ated at a flow rate of 167 litersmin (1min) Teflon filters (37 mm
diameter and 2 microm pore size were purchased from Membrana Inc
Pleasanton CA and were changed manually every 2 hours for a total
collection period of 24 hours At Berkeley and Martinez air samples
were collected using an automatic dichotomous sampler (32) provided by
the Lawrence Berkeley Laboratory (LBL) Berkeley CA Filters were
37 mm diameter 1 microm pore size and came mounted on plastic frames
(Membrana Inc Pleasanton CA) The sampling flow rate was
50 litersmin
Dichotomous filters were extracted by sonication in a mixture of 111
methanol dicholoromethane and toluene (trisolvent) as previously described
(33) Filters were extracted in 16 x 125 mm screw-top glass tubes 4 ml
of extraction solvent was added to each tube which was then sealed with
a Teflon-lined screw cap and placed in an ultrasonic water bath at 45degc
After sonication at maximum power for 20 minutes the extract was
passed through a 05 micro m Fluoropore filter The filter was washed again
with 3 ml trisolvent by sonication the extract filtered and combined with
the initial filter extract The volume of the combined extract was
decreased tenfold in vacuo by rotary evaporation at 45degc and the extract
was transferred to a 1 dram vial evaporated under a stream of nitrogen
to dryness capped under nitrogen and stored at -20degC until tested All
extraction procedures were carried out under yellow fluorescent lights to
minimize potential photooxidation
Lead in dichotomous filter samples was determined by atomic absorption
spectrophotometry (34) A sample 10 mm in diameter from the center
-14-
of the filter was extracted in 10 nitric acid and the extract analyzed
for lead with a Perkin-Elmer Model 503 Atomic Absorption Spectrometer
4 Mutagenicity Assays
All mutagenicity testing was done using frame shift tester strain TA98
(35) and nitroreductase deficient derivative T A98NR (36) The standard
plate incorporation method for detecting mutagens with the Salmonelshy
lamammalian microsome test was performed as described by Ames et
al (12) A liver extract prepared from male Spraque Dawley rats
(150-200g) treated with Aroclor 1254 was prepared according to the method
of Ames et al (12) The protein concentration was 30 mgml determined
by the method of Lowry et al (37) A simple modification of the
Salmonella liquid incubation procedure reported by Kado et al (19) was
used throughout
Single colonies were taken from a master plate made from Oxoid Nutrient
Broth (Oxoid Ltd Hants England) added to 10 ml of Oxoid Nutrient 9broth and gown overnight to a concentration of approximately 1-2 x 10
cells per ml Cells were concentrated by centrifugation (10000 X g
4degC) 10 minutes and resuspended in ice-cold phosphate buffered saline 10
(PBS 015M pH 74) to a concentration of 1 X 10 cells per milliliter
The microsuspension procedure was performed with metabolic activation
(+S9) by adding the following ingredients in order to 12 X 75 mm sterile
glass culture tubes placed in ice 01 ml S9 mix 0005 ml of DMSO
solution containing the test material and 01 ml of concentrated bacteria
1010(approximately 1 X per ml PBS or 1 X 109 per tube) A similar
mixture was prepared to test samples without the addition of metabolic
enzymes (-S9) except that the sample (in DMSO) was added to the
concentrated bacterial solution first followed by the addition of 01 ml
phosphate buffer (0lM pH 74) The tubes were capped and incubated
in the dark at 37degC with rapid shaking After 90 minutes the tubes
were placed in an ice water bath removed singly from the ice bath and
2 ml of molten top agar containing 90 nmoles of both histidine and biotin
were added The molten suspensions were immediately mixed with a
-15-
Vortex mixer and poured into minimal glucose plates Plates were
incubated at 37degC in the dark for 48 hours and were counted using an
automatic colony counter (Biotran III New Brunswick Scientific Edison
NJ) Genetic markers for the strains were routinely verified Mutageshy
nicity testing was carried out in a room fitted with yellow fluorescent
lights to minimize potential photooxidation
Duplicate aliquots of all mutagen standards and extracts of air particulate
matter were tested at 3 or more doses
D Results and Discussion
1 Chemical Mutagens
Mutagenic activities of the chemical mutagens 2-nitrofluorene (2-NF)
4-nitroquinoline-N-oxide (4-NQO) 2-aminofluorene (2-AF) and benzo(a)shy
pyrene (BaP) were determined by the standard plate incorporation assay
and the microsuspension procedure The microsuspension procedure
measured rnuch higher levels of specific mutagenic activity for each
chemical the activity of 2-NF increased most dramatically by a factor
greater than 30 (Table II-1) There was little increase in the number of
spontaneous revertants in the microsuspension procedure although ten times
more bacterial cells were added For example the solvent blanks in
TA98 for the microsuspension and standard Ames assays (-59) were 29
and 17 revertants per plate respectively This can be explained as follows
The number of spontaneous revertants is related to the total number of
cell divisions which occur during 48 hours of incubation In both assays
approximately the same total number of divisions occur because growth
is limited to the same extent by the available histidine Since ten times
more cells are added initially in the microsuspension procedure fewer
divisions per cell take place by the time the final (histidine-limited) cell
density is reached However in the plate incorporation test there are
initially fewer cells added per plate but more divisions per cell Thus
the total number of divisions and therefore the number of spontaneous
revertants which occur in both procedures are similar
-16-
TABLE 11-1
COMPARATIVE MUTAGENIC ACTIVITY OF MUTAGENS IN THE PLATE INCORPORATION AND MICROSUSPENSION PROCEDURES
Specific Mutagenic Activitya (TA98 revnmol)
Chemical Plate
Incorporation Micro-
Suspension
Fold Increase in Sensitivity
Benzo(amicroyrene 93 907 10
2-Aminofluorene 199 2460 13
2-Nitrofluorene 61 1940 31
4-Nitroquinoline-N-oxide 103 1800 18
aDetermined from the linear portion of the dose-response curve from a single
experiment
-16a-
The direct-acting mutagens 2-NF and 4-NQO were 20-30 times more
mutagenic in the microsuspension procedure than in the plate incorporation
assay and the indirect-acting mutagens BaP and 2AF were approximately
10 times more mutagenic The results for BaP are in good agreement
with the previous study (19) where the microsuspension procedure was
about 14 times more sensitive We also investigated the applicability of
the microsuspension procedure to a related tester strain TA98NR As
shown in Table II-2 the mutagenic activity of 2-NF decreased appreciably
when it was tested in TA98NR but the activity of 4-NQO remained
approximately the same These responses are similar to those reported
by Rosenkranz and Mermelstein (38) for the plate incorporation test The
mutagenic activity of the pooled air extract also decreased from 24 3 3 rev m to approximately 4 rev m indicating that compounds similar to
2-NF may be responsible for most of the direct-acting mutagenic-activity
in this sample The increased sensitivity of the microsuspension procedure
for both direct and indirect-acting mutagens is probably due to the
combined effects of increasing the total number of bacteria added and
concentrating the incubation mixture including the sample in a small
volume (02 ml) The formef increases the concentration of bacterial
DNA targets available for interaction with mutagens and the latter
increases the likelihood of mutagens being taken up by the cells
2 Hi-vol Air Particle Extracts
Dose response curves for mutagenic activity of the composite hi-vol air
particle extract constructed from the plate incorporation test and from
the microsuspension procedure are illustrated in Figure Il-1 The amount
of extract added is expressed in units of cubic meter equivalents the
number of cubic meters of sampled air containing a specific amount of
particulate matter One cubic meter equivalent (m3 equivalent) is approxishy
mately equal to 17 microg of particulate matter for the composite sample
The extract added per plate in the microsuspension procedure and plate 3incorporation test respectively was 1-11 m equivalents (23-185 mg of
3particulate matter) and 5-43 m equivalents (92-739 mg of particulate
matter) The optimal levels of S9 determined to be 600 microg proteinplate
-17-
TABLE 11-2
COMPARISON OF DIRECT MUTAGENIC ACTIVITY OF 2-NITROFLUORENE 4-NITROQUINOLINE-N-OXIDE AND COMPOSITE BERKELEY AIR FILTER
EXTRACT IN TA98 AND TA98NR AS DETERMINED BY THE MICROSUSPENSION PROCEDURE
Specific Mutagenic Activity8
Test Substance TA98 TA98NR
2-Nitrofluorene (rev nmol) 4170 405
4-Nitroquinoline-N-oxide 1540 llBO
(revnmol)
Composite Berkeley
Air Filter Extract 24 4
(revm3)
aCalculated from dose-response curve using pooled data from 2 experiments
-17a-
FIGURE II- 1 Dose-response curves for composite hi-vol air particle extract Determined using the plate incorporation test and microsuspension procedure with (a) and without (b) rat liver S9
1000
(a)+ S9
UJ E-lt -l 0
800
__ bull Microsuspension (f)
600E-z lt E-0 UJ gt
400
Ul 0
00
deg 200lt E-
0 ----~P----------------~------ 0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
400 UJ (b) - S9Eshylt -l 0
(f)
Eshyz lt E-0 Ul gt Ul 0
deg lt E-
300
200
100
Microsuspension
0
Plate Incorporation
0 _________________ ______
0 10 20 30 40 50
CUBIC METER EQUIVALENTS PLATE
-17b-
00
for the standard plate incorporation test and 30 micro g proteinplate for the
microsuspension procedure were used for all the tests As illustrated in
Figure II-1 the microsuspension procedure was approximately 10 times
more sensitive than the plate incorporation test both with and without
metabolic activation The respective slopes for the microsuspension 3procedure with and without S9 were approximately 60 and 26 rev m
while the corresponding slopes for the plate incorporation test were 6
and 3 rev m3 A response was considered positive if it was at least
twice the number of spontaneous revertants The microsuspension proshy
cedure and the plate incorporation assay required air samples of approxishy3 3mately 1 m and 10 m respectively to achieve this doubling The
concentrations of total suspended particulates in the air samples used to
prepare the composite were between 50-100 microgm 3bull The amount of S9
protein required per plate in the microsuspension procedure was oneshy
twentieth that needed in the plate incorporation test These results are
consistent with those obtained during the analysis of urine from cigarette
smokers reported previously (19)
3 Diurnal Variations in Mutagenicity of Fine Particle Extracts
Data on diurnal variations in mutagenicity were obtained from two-hour
samples collected by dichotomous samplers The first of the three diurnal
studies was done in Rodeo California Two-hour samples were collected
during the 24 hours beginning at 6 am August 27 1982 using a Sierra
manual dichotomous sampler at a flow rate of 167 liters per minute
Filters were changed manually every 2 hours As illustrated in Figure II-2
mutagenic activity was detected with metabolic activation (+S9) in extracts
of the fine fraction ( lt25 micro m) and a distinct diurnal pattern of mutagenishy
c ity can be seen with a morning peak of activity between 10 am and
12 noon and an evening peak between 8 and 10 pm In this experiment
activity was not detected in the fine fraction extracts in the absence of
S9 and none was detected in the coarse fraction extracts whether or not
S9 was present The diurnal variations in mutagenic activity in the Rodeo
extracts although not especially large encouraged us to carry out a
second study under circumstances where higher activities were anticipated
-18-
I I- oi Pl I
200 ---------------------------------
-
150 -
100 -
Rodeo Calif Fine +S9
~f~t~fWW
50 lI
0 middot middotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot middotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddotmiddot
6am 10am 2pm 6pm 10pm 2am
TIME OF DAY
FIGURE II- 2 Diurnal variation of mutagenicity of fine airborne particles collected in Rodeo California and measured in the microsuspension procedure A single four hour sample was collected between midnight and 4 am
M e ()
~ z ltt ~ er IJJ gt IJJ 0 00 OI ltt ~
r IJJ z
6am
The second experiment was conducted in Berkeley on October 20-21 1982
Two-hour samples of size-segregated air particles were collected with an
automatic dichotomous sampler (ADSLBL Model I) located in a service
yard outside the California Department of Health Building in downtown
Berkeley and operated at a flow rate of 50 1min The diurnal variations
observed are depicted in Figure 11-3 Mutagenic activity of fine particle
extracts from the samples ranged from less than 75 to nearly 600 revertants
per cubic meter of air sampled Similar diurnal patterns of mutagenic
activity were detected both with and without metabolic activation the
+59 response being approximately three times higher Virtually no activity
was detected in the coarse particle extracts The maximum level of
activity measured in Berkeley was about four times higher than that
measured in Rodeo and the diurnal patterns were similar at both locations
A morning mutagenicity peak occurred between 10 am and 12 noon and
an evening peak between 10 pm and 2 am Both the morning and
evening peaks appeared later than peak traffic flow (7-8 am and 5-6 pm)
The success of these first two trials prompted a third field study in which
levels of mutagenicity and criteria air pollutants were measured simultashy
neously to better define the possible sources of activity
Air sampling for a third field trial was conducted at the Mountain View
Sanitary Districts facility in Martinez California during the 36 hours
beginning at 6 pm November 3 1982 The criteria air pollutants samples
were lead (Pb) nitrogen dioxide (NO2) ozone (0 ) and sulfur dioxide3 (50 ) The two-hour particulate samples analyzed for mutagenicity and2 lead were collected with the LBL Model 1 Automatic Dichotomous Sampler
(ADS) only the fine fractions were analyzed Gaseous pollutants were
monitored continuously and hourly averages were calculated and used for
comparisons Twelve-hour hi-vol samples were collected simultaneously
at the site
The results are illustrated in Figure 11-4 Peak levels of mutagenic activity
both with and without S9 were found in the early morning around 6 am
and around midnight Maximum values measured in the presence of
metabolic activation were greater than 1000 revertantsm3 air
-19-
FIGURE II- 3 Diurnal variation of mutagenicity of fine airborne particles collected in Berkeley California and measured in the microshysuspension procedure with (a) and without (b) addition of rat liver S9
E
(JJ fshyz lt f-c tJJ gt uJ c 00
deg lt f-
EshyuJ z
800 ---------------------------------~
-
600 -
-
400 -
-
200 -
Berkeley Calif Fine +S9
1------1
10am 2pm
llllilililililiiiliilllIIIIIIIIIIIIIIIIIII
6pm
TIME OF DAY
Cl C
E
C
E (J
10pm 2am 6am6am
800 -------------------------------
Berkeley Calif - Fine -S9
E
600 -(JJ
Eshyz
-lt EshyC tJJ
400 -gt tJJ c
deg 00
lt -
E-
EshytJJ z
11111111111111111
l
10am 2pm 6pm 10pm 2am 6am
TIME OF DAY
-19a-
6am
FIGURE II- 4 Diurnal variation of mutagenicity of fine airborne particles collected in Martinez California and measured in the microsuspension procudure TA98 with S9 (a) TA98 without S9 (b) TA98 NR without S9 (c)
1200
1000 E
_ ltJ)
1-- 800 z ltC 1--CZ UJ 600gt UJ CZ
00 c
400ltC 1--
1--UJ z 200
0
Martinez Calif Fine +S9
7pm 11pm 3am 7am 11am 3pm 7pm 11pm 3am 7am
TIME OF DAY
1200 --------------------------------
Martinez Calif Fine -S91000
degE _ ltJ)
1-- 800 z ltC 1--c ~ 600 UJ 0
00
~ 400 I-I--UJ z 200
0
7pm 11pm 3am 7am 11am 3pm 7pm 11 pm 3am 7am
TIME OF DAY
200 ---------------------------------
Martinez Calif Fine TA98 NR -S9
150 (I)
1-shyz ltC 1--0 UJ
100gt UJ 0
00 c ltC 1--
1-shy so UJ z
0
7pm 11pm 3am 7am I lam 3pm 7pm 11pm 3am 7am
TIMEOF DAY
-19b-
Mutagenic activities of the hi-vol samples taken in parallel with the
dichots were compared to the calculated average activities of the dichots
As summarized in Table II-3 the calculated average activities of the
dichotomous samples are similar to the activities of the hi-vol sample
Although the average mutagenic activity of the dichot is slightly higher
for the two nighttime periods especially for mutagenic activity dependent
on metabolic activation these differences are within experimental error
The diurnal pattern of fine fraction lead (not shown) was very similar to
that of mutagenicity exhibiting both early morning and late night peaks
Lead and mutagenicity are strongly correlated (r = 92) as shown by the
plot of sample values in Figure U-5 Since motor vehicles are the primary
source of airborne lead this correlation suggests that they are also the
source of much of the airborne mutagenic activity
Diurnal patterns of the three measured gases (o3 so2 N0 ) did not2 correlate well with mutagenic activity Only lead concentrations were
related to concentrations of particulate mutagenicity
The present results may be compared with those of Pitts and coworkers
(2229) In their studies diurnal comparisons were made of airborne
mutagencity of Los Angeles air using 3-hour hi-volume samples They
found that mutagenic activity was strongly correlated with carbon
monoxide (CO) emitted principally from automobile emissions in Los
Angeles air and that mutagenic peaks were closely related to peak
commuting hours In the present study mutagenic peaks appeared later
than would be expected from diurnal patterns of traffic flow near the
sampling sites
Our conclusion that mobile source emissions contribute significantly to
the mutagenicity of airborne particles sampled in Martinez is consistent
with results of a related study which investigated sources of particulate
matter collected at four Contra Costa County locations during seasonal
pollution episodes in 1981-82 (1839) Air samples were analyzed for
-20-
TABLE 11-3
MUTAGENICITY OF PARTICLES COLLECTED BY HI-VOLUME AND DICHOTshy
OMOUS AIR SAMPLERS RUN IN PARALLEL AT MARTINEZ CALIFORNIA
Mutagenic Act~ity (TA98 revm )
+59 -59
Sampling Hi-Vol8 Dichotb Hi-Vol8 Dichotb Period (Ave) (Ave)
1920-705
(113-11482)
710-1915
(11482)
2020-705
(114-11582)
572 723 223 238
304 236 101 86
624 727 238 296
aMutagenic activity determined from linear portion of dose-response curve
bMutagenic activity is the average number of revertants per cubic meter for the 12
hour sampling period calculated from six consecutive 2-hour sampling periods
-20a-
bull bull
1200
M 1000
I _
t- bulls bull bull f) t-h-z BOO~ ~
bull middot-
er uJ 600 1 gt uJ
N I er
0 cr I I00
OI bull400
~ -
-uJ z 200
bull bullI
0 0 05 1 15 2
LEAD (microgm3)
FIGURE II- 5 Correlation of airborne lead and mutagenicity (microsuspension procedure with S9) from fine particles collected at Martinez California sampling site r = 092
mutagenic activity and a variety of particulate chemical pollutants and
gases Mutagenicity was found to be strongly associated with leadshy
containing fine particles
The present study is also in agreement with previous studies on sizeshy
segregated particles in which investigators found that most of the
mutagenic activity is associated with particles of diameters of about
2 microm or less (4041)
E Conclusions
This study presents data on diurnal variations in mutagenicity of community
aerosols of less than 25 microm aerodynamic diameter in samples of 2 hour duration
In field studies diurnal variations in mutagenic activity (revertantsm3) of 10
fold were found Variations in mutagenic activity correlated well with the
variations in fine-fraction lead implicating motor vehicles as a significant source
of mutagens These experiments were made p0ssible by the use of the highly
sensitive microsuspension modification of the Salmonella liquid incubation assay
This modification makes possible high resolution diurnal studies of fine aerosols
and can be applied in future studies where sample mass is a limiting factor
-21-
CHAPTER ill
SOURCES OF MUTAGENS AND POLYCYCUC AROMA TIC HYDROCARBONS IN
CONTRA COSTA COMMUNITY AEROSOLS DURING POLLUTION EPISODES
DIURNAL GEOGRAPHIC AND EPISODE VARIATIONS
A Introduction
As described previously applications of the Ames Salmonella test (12) to commushy
nity air particles have demonstrated that chemical mutagens are ubiquitous
components of urban aerosols (1-6) A fundamental problem concerns source
identification The measure of a relatively high mutagenic activity in a given
geographical area is of limited value unless the sources of the mutagenicity can
be identified and therefore potentially controlled In a previous CARS-supported
air pollution study in Contra Costa County AIHL measured mutagenicity and a
variety of chemical air pollutants (18) The study examined diurnal variations
of mutagenic activity and the relationship of mutagenic activity to other aerosol
variables including certain source tracer elements The results indicated that
mobile sources were significant contributors to PAH and particulate mutagens
The present study extends this earlier research using the same experimental
approach
B Experimental Methods
1 Air Sampling and Site Descriptions
Six 36 hour sampling episodes were carried out in Contra Costa County
during periods of high pollution in 1982-1984 Samples were collected at
four locations in Richmond Martinez Concord and Pittsburg (Figure I-2)
Three (Richmond Concord and Pittsburg) are located so as to reflect the
quality of outdoor community air breathed by the public These three
are permanent stations of the Bay Area Air Quality Management District
(BAAQMD) The fourth site at a temporary location in the Mountain
View Sanitary District Martinez is specifically located to sample industrial
emissions The Concord site is near the intersection of two major streets
-22-
with a combined daily traffic count of approximately 50000 in a residential
and commercial area The Richmond site is close to a major city street
with a daily traffic count of 30000 Industry is located 3 km miles west
of the site The Pittsburg site is adjacent to a roadway with a daily
traffic count of 10000 and is about 1 km south of an oil burning electrical
power plant The Martinez site is located about 600 m from a petroleum
refinery complex which is to the north and west Approximately 250 m
east of the site is a freeway where the daily traffic counts is 60000
Residential tracts are also nearby
At the three permanent stations the samplers were placed on the roof
tops of one story buildings approximately 8-10 m vertically and 25-40 m
horizontally from the nearest roadway At Martinez the samplers were
at ground level (1 m) Each location had two hi-vol samplers and one
dichotomous sampler to collect particulates for chemical and mutagenic
analysis Gaseous pollutants (CO so2
NO NO and o ) were also2 3
measured During the 36 hour episodes separate 12 hour daytime (0600-
1800 and nighttime (1800-0600) samples were collected in order to compare
diurnal differences
Air particulate material for mutagenic and PAH testing was collected on
glass fiber filters (Whatman) in standard hi-vol samplers The filters were
used as supplied from the manufacturer and were not pre-treated in any
way Filter-solvent blanks were routinely assayed for mutagenicity and
the responses were below detection Dichotomous fine ( lt25 micro md ) and a
coarse (25 microm - 15 micromd ) fraction particulate samples were collected a
for multielement analysis on 37 mm Teflon Fluoropore (02 micron) filters
(Ghia) in standard dichotomous samplers (Anderson and Sierra Models)
2 Meteorological Measurements
Temperature and inversion conditions in Contra Costa County during the
episodes were inferred from data collected at the Oakland Airport which
is located approximately 25 km from the nearest sampling station Oakland
measurements were made twice daily at 0400 and 1600 hours PST In
-23-
addition hourly average wind speeds and wind directions were obtained
at Martinez These meteorological data permitted quantitative characshy
terization of weather conditions but were insufficient to permit accurate
descriptions at individual sampling sites Consequently upwind-downwind
relationships to roadways adjacent to the sites could not be established
3 Chemical Analysis
Air pollutant variables are defined in Table I-1 and the methods used
listed in Table I-2 Measurement of trace elements (eg Pb Zn Fe
Ni) on fine and coarse particulate samples collected with dichotomous
aerosol samplers was done by x-ray fluorescence analysis (42) Analyses
of the standard particulate pollutants (TSP so = N03
- Organics) colshy4 lected on hi-vol filters were carried out as previously described (18)
Gaseous pollutants were continuously monitored using specific gas monitors
o was measured by ultraviolet absorption CO by infrared absorption3
NO and N0 by chemiluminescence and so by fluorescence detection2 2 All methods are EPA reference or equivalent to the EPA reference methods
(2831)
PAH were determined as previously described (18) Sample clean-up steps
were omitted with no loss in resolution Filters were extracted ultrashy
sonically in trisolvent (toluenemethylene chloridemethanol(l11)) (MCB
Omni-Solv) PAH were separated by HPLC and identified by specific
fluorescence and ultraviolet absorption In addition the presence of
benzanthrone (7-H-benz(de)anthracene-7-one) was confirmed by mass
spectral analysis (18)
4 Mutagenicity Testing Methods
Following collection filters from episode sampling were stored for up to
three months at less than -10degC in the dark Standard methods for
extracting air particulate material from filters for mutagenicity testing
were used (18) Extractions with trisol vent were carried out under reduced
light in an ultrasonic bath and extract residues redissolved in dimethyl
sulfoxide (DMSO) for mutagenic analysis Extracts were stored for 24-48
-24-
hours at -10degC The standard plate incorporation Salmonellamammalian
microsome test was used (12) Mutagenic responses were determined both
with and without rat liver homogenate (S9) in strain T A98 which responds
mainly to frame-shift mutagens and in TA98NR a nitroreductase deficient
derivative (36) A commercial preparation (Litton Bionetics) of Aroclor
1254 induced rat liver S9 was used Direct-acting mutagens are detected
without S9 and both direct-and indirect-acting mutagens are detected in
the presence of S9 although the activities of some direct-acting chemicals
are decreased by the addition of S9 The term indirect mutagenicity
operationally defines the response of the Ames test in the presence of
S9 Ames test results were reported as mutagenic density (revertants
produced by the extract from the particles in one m 3 of air) or mutagenic
specific activity (revertants per microg benzene soluble organics) Reduced
responses of air extracts in T A98NR suggest contributions from ni troarenes
5 Statistical Methods
Statistical analysis was based on programs contained in the Statistical
Analysis System (SAS) (43) run through the California State Health and
Welfare Data System
Correlation analysis was done to relate mutagenicity and PAH variables
with selected chemical pollutants Emphasis was on fine fraction aerosol
variables since mutagens are found on small particles ( lt25 micromd )a
Factor analysis was used to help identify principal types of emission
sources Factor analysis was carried out using the principal component
method on a correlation matrix of selected variables (fine fraction trace
element concentrations NO - mutagenicity and PAH variables) After3
several preliminary trials factors with a minimum eigen-value of 07 were
chosen to be induced in the principal factors The principal factors
retained with this criterion were then used in a varimax rotation procedure
-25-
C Results and Discussion
l Meteorological Conditions during Episodes
As noted above temperature and inversion information were collected
twice daily (at 0400 and 1600 hours PST) at the Oakland Airport while
wind speed and wind direction were measured at the Martinez sampling
site The wind directionwind speed data at Martinez are included in
Appendix I San Francisco Bay Area weather factors measured during
the episodes by the Bay Area Air Quality Management District are also
provided in Appendix II These data permit the following qualitative
descriptions of meteorological conditions prevailing during each episode
Episode I
Sampling was carried out from 0600 on August 23 to 1800 on August 24
1982 Two day and one nighttime periods were sampled At Martinez
winds were from the west throughout the episode at speeds averaging 11
mph by day and 8 mph by night Oakland surface temperatures were
relatively cool reaching a daytime maximum of only 69degF The minimum
was 59degF at night The base of a shallow inversion at Oakland was 262 m
at 0400 hours PST August 23 and 503 m at 1600 hours PST August 24
Episode II
Two night and one daytime periods were sampled beginning at 1800 on
October 12 and ending at 0600 on October 14 1982 At Martinez winds
were very light (2-4 mph) throughout and from the south-west during the
first night shifting to the east during the day and becoming westerly
during the second night a daytime surface temperature maximum of 76degF
was recorded The minimum was 52degF Oakland inversion data were
limited at 0400 hours PST October 13 and 1600 hours PST October 14
the inversion base was at the surface
-26-
Episode III
Two night and one daytime periods were sampled beginning at 1800 on
May 17 and ending at 0600 on May 19 1983 This episode was carried
out during a period of high insolation Winds were light (3-4 mph) and
from the west throughout at Martinez The Oakland inversion base was
162 m at 0400 hours PST May 17 at the surface at 1600 hours PST May
18 and 66 m at 0400 hours PST May 18 The maximum and minimum
surface temperatures at Oakland were 73degF and 55deg respectively
Episode IV
Two night and one daytime periods were sampled beginning at 1800 on
September 12 1983 and ending at 0600 on September 14 1983 Westerly
breezes prevailed at Martinez throughout the episode averaging 2 mph
during the first night and 6-7 mph during the remaining periods The
base of the Oakland inversion was at the surface at 1600 hours PST and
0400 hours PST September 12 and again at 1600 hours PST on September
13 Oakland surface temperatures were hot (94degF) just prior to the start
of sampling (1500 hours PST September 12) and fell to 59degF near the
end of the period
Episode V
Two night and one daytime periods were sampled beginning at 1800 on
October 4 and ending at 0600 on October 6 1983 Again light westerly
winds prevailed at Martinez throughout with the Oakland surface tempershy
ature reaching a daytime maximum of 76degF and falling to a minimum of
58degF at night At 0400 hours PST on October 4 the inversion base was
651 m at 1600 hours PST on October 5 the inversion base was llO m
Episode VI
In the final episode two night and one daytime periods were sampled
Sampling was carried out from 1800 on January 4 to 0600 on January 6
1984 Martinez winds averaged 5-7 mph and were from the east throughout
Oakland surface temperatures were cool with a maximummiddot of 56degF and a
-27-
minimum of 46degF Oakland inversion data were 0400 hours PST January
4 base = 181 m 0400 hours PST January 5 base = surface 0400 hours
PST January 5 base = 89 m
Episode Summary
Considering middot the six episodes as a whole one generality concerning
meteorology emerged With the exception of episode VI the overall
direction of the surface winds was from the west so areawide transport
of pollution should be from Richmond on the west through Martinez
towards Concord and Pittsburg on the east
2 Combined Episode Data with Diurnal Comparisons
Initially we combined all results of air pollution measurements made during
the six intensive sampling episodes in 1982-1984 for statistical analysis
The combined data set contained 72 observations of mutagenici ty and
chemical pollutant measurements These data were separated into daytime
and nighttime periods for diurnal comparison Because of the sampling
strategy more observations were made at night (N=44) than during the
day (N=28) At the outset our strategy in sampling episodes was to
collect at least one daytime and one nighttime sample Therefore we
sampled for 36 instead of 24 hours to improve the chances of obtaining
a complete set of samples for two consecutive 12 hour periods The
consequence of having collected samples over 3 consecutive periods was
that we analyzed all samples and subsequently have included all sample
test results in the statistical analysis The advantage of using all the
results is that we have added one-third more observations to the data
base a substantial increase The disadvantage is that the data do not
contain equal periods of day and night
Therefore to calculate means for the combined data based on equal
periods of day and night results of the twice-sampled (usually the
nighttime period) were averaged and then combined with results of the
once-sampled period The method of treating this inequality in this
-28-
report is different than the method used in the first report on mutagenicity
in Contra Costa County (18) The different methods are as follows
D + d 2 + N
Present report Mean = 2
where D d are daytime values and N is a nightime value
D + d + N + NPrevious report Mean = 4
where N the once-sampled period is entered twice
Both methods give the same mean values however the ranges obtained
using the present method are reduced somewhat due to the averaging 3
procedure For example in Table III-1 the maximum value of 44 revm
is listed for combined episode data even though during one 12 hour period
a value of 58 revm3 was measured
For correlation and factor analysis the unmodified data were used Since
there are more nighttime than daytime observations the correlations and
factor patterns for the combined episode data reflect larger contributions
from nighttime sources
Summary Statistics
Mean concentrations and other summary statistics for the six episodes
combined are shown in Table III-1 Note that the typical sample size
shown in the tables (N = 24) is smaller than the actual number of samples
collected because of the averaging procedure used to calculate the
summary statistics The 1981-82 (three) episode statistics for the air
pollution variables discussed below are shown in Table III-2 so the difshy
ferences with time can be compared Variables which are statistically
significantly different between the two studies (p 2 005) are indicated
with an asterisk in Table III-I (To test the equality of means for mutagens
densities and other pollutants between 1981-1982 episodes and 1982-1984
-29-
TABLE III-1
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES COMBINED DATA 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 24 21 11 3 44
M398MS9 3revm 24 9 5 l 21
ORG98PS9 rev microg 23 10 8 ltl 30
ORG98MS9 rev microg 23 5 4 ltl 14
M398NRM 3revm 16 4 l 2 7
NR98M3 16 036 014 015 068
BAP 3ngm 24 02 02 01 08
BKF 3ngm 24 01 01 01 04
BGP 3ngm 24 09 06 02 26
COR 3ngm 24 06 04 01 15
BZO 3ngm 24 08 07 01 32
ORG microgm3 23 35 2-4 1-5 8-4
TSP 3microgm 23 64 21 24 124
NO -3
so=4
BRF
microgm 3
microgm 3
3ngm
23
23
24
79
86
45
40
44
29
32
50
9
182
223
117
PBF 3ngm 24 242 153 52 605
BRFPBF 24 020 008 013 041
ZNF ngm3 24 26 13 9 68
KF 3ngm 24 142 103 50 429
FEF 3ngm 24 128 88 26 357
SIF 3ngm 24 291 235 56 952
CLF ngm3 24 260 426 27 2173
NIF 3ngm 24 7 6 2 27
SF 3ngm 24 1797 1195 516 6473
co ppm 18 11 04 05 17
NO pphm 21 19 12 03 43
NO2 pphm 23 26 11 09 49
03 pphm 23 22 11 01 41
502 pphm 23 04 07 00 34
Mean significantly different (p ~ 005) from mean during 1981-82 episodes
-29a-
TABLE ID-2
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM THREE EPISODES COMBINED DATA 1981-1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 12 12 6 6 21
M398MS9 3revm 12 7 2 3 10
ORG98PS9 revmg 12 2 3 ltl 8
ORG98MS9 revmg 12 l 1 ltl 3
M398NRM 3revm 12 3 l ltl 5
NR98M3 12 043 016 018 071
BAP 3ngm 12 06 06 01 16
BKF 3ngm 12 03 02 01 07
BGP 3ngm 12 14 11 04 34
COR 3ngm 12 08 05 02 19
BZO 3ngm 12 21 20 03 58
ORG 3ngm 12 75 35 20 107
TSP 3microgm 12 90 22 52 126
NO3 so4 BRF
3microgm
3microgm
3ngm
12
12
11
115
149
69
46
57
48
41
53
16
185
252
172
PBF 3ngm 11 262 162 82 671
BRFPBF 11 025 007 015 040
ZNF 3ngm 11 37 13 12 55
KF 3ngm NA
FEF 3ngm 11 102 39 42 155
SIF 3ngm NA
CLF 3ngm NA
NIF 3ngm 11 25 14 7 51
SF 3ngm NA
co ppm 9 12 05 06 19
NO pphm 9 28 22 07 63
NO2 pphm 9 36 15 10 61
03 pphm 9 16 14 01 40
so2 pphm 9 04 03 0 09
NA = Not analyzed
-29b-
episodes t-tests were carried out Appropriate t-statistics were chosen
based on the results of F-tests on equal variances If the variances were
equal t-statistics derived from pooled variances were used Otherwise
t-statistics derived from separate variances were used)
The combined six episode mean for mutagenic density in T A98 was
21 revm 3 (with S9) and 9 revrn 3 (without S9) Thus both direct and
indirect acting mutagens are present The value with S9 is significantly
higher than the mutagenic density previously measured during pollution
episodes in 1981-82 (12 revm3 +S9) (18) In the present study the mean
mutagenic density in the nitroreductase deficient strain TA98NR (-S9) 3 ~as 4 revm and the ratio of TA98NRTA98 was 036 both values are
similar to those measured in the earlier study Thus more than half of
the mutagenic activity of aerosol extracts is dependent upon enzymatic
nitroreduction This implies that mononitroorganics such as 1-nitropyrene
which are known to be present in community aerosols elsewhere (1517)
probably make major contributions to the mutagenicity of Contra Costa
aerosols
Mean mutagenic specific activities (rev microg ORG) were 10 (+S9) and 5
(-S9) These are both significantly higher values than those measured in
1981-82 (cf Table III-2) Note that significantly lower benzene soluble
organic concentrations were also found in the present study The mean 3organic concentration measured (35 microgm ) was approximately a factor
of two lower than that measured in the 1981-82 episodes (75 microgm 3)
Thus although the organics in general have dropped the organics that
remain are much more mutagenic Among PAH levels of BAP and BZO
were also significantly lower than previously measured In the present 3study concentrations ranged from the detection limit (01 ngm ) for BKF
and 02 ngm 3 for BAP to 09 ngm 3 for BGP
The mean episode TSP level in the present study wasmiddot 64 microgm 3 signifishy
cantly lower than previously found In 1981-82 the episode mean TSP 3
value was 90 microgm bull These results indicate that mutagenic density has
increased despite decreasing TSP and aerosol organic levels Increasing
mutagenic specific activity over time is of potential concern to public
health and is analyzed in greater detail in Chapter IV
-30-
Mean concentrations of NO - and SO = were 79 and 86 microgm 3 respecshy3 4
tively also significantly lower (by approximately 40 percent) than those
observed in 1981-82 The Hi-Vol so - concentration was comparable to4
the so value calculated from the fine fraction sulfur concentration4
=
(l8 microgm 3) (Only about 10 percent of S (02 microgm 3) was found in the
coarse fraction) Assuming all of the fine S is in the form of SO the4 -
mean fine fraction so concentration was calculated to be approximately4
=
54 microgm 3 or two-thirds the amount of so4
= found by the Hi-vol method
Among gaseous pollutants the mean CO concentrations was 11 ppm
Means of NO NO and o were 19 26 and 22 pphm respectively The2 3
mean so concentration was 04 pphm These gas concentrations are2
similar to those measured earlier in Contra Costa although NO2 concenshy
trations were significantly lower Pitts and coworkers have recently
described a possible filter sampling artifact related to o (23) Increased3
mutagenicity was measured when aerosols were collected on glass fiber
filters in the presence of higher o concentrations (gt 10 pphm) However3
o concentrations measured in Contra Costa County were all below those3
which produced significant artifacts in the study of Pitts et al which
was carried out in El Monte and Riverside
Among aerosol trace elements fine fraction lead concentration was 242
ngm 3 very near to the mean concentration measured in 1981-82 episodes
(262 ngm3) Fine fraction Br was 45 ngm3 and the BrPb ratio was
02 indicating the presence of an aged aerosol Ratios in fresh auto 3
emissions are typically greater than 03 Fine fraction Zn was 26 ngm
significantly below the 1981-82 value (37 ngm3) The fine fraction iron
concentration (128 ngm3) was comparable to the 1981-82 value
(102 ngm 3) The fine fraction Ni concentration was 25 ngm 3 in the
previous study and 7 ngm3 in the present investigation We can provide
no explanation for the significant threefold decrease in Ni Among other
trace elements the mean fine fraction potassium concentration was 142
ngm 3 The KFe ratio of 11 is higher than typically seen in soil (05)
but much lower than in aerosols derived primarily from wood combustion
(gt8) (44)
-31-
For most variables the diurnal differences (cf Tables IIl-3 and 4) were
small Mutagenic density (+59) was slightly higher by day (24 revm 3) 3than by night (17 revm ) However direct-acting (-59) mutagenic density
was nearly constant from day (10 revm 3) to night (9 revm 3) Organic
levels (total and specific PAH) were also very similar from day to night
TSP and NO were both slightly higher by day while so showed4 = 3 essentially no diurnal change
Two measured pollutants CLF and o3 exhibited clear diurnal differences
Fine fraction chloride (CLF) was twice as high at night while o was3 twice as high by day (cf Tables III-34) The difference in CLF may
be related to diurnal differences in relative humidity The o difference3
reflected daytime photochemical formation of ozone in the atmosphere
Correlation Analysis
Correlation analysis was carried out to explore relationships between
mutagens PAH and source emissions tracers Correlations between mutashy
genic density PAH and selected elements and gases are shown in Tables
III-5-7 (Complete correlation matrices are provided in the Appendix III)
Mutagenic density variables (t59) were very strongly correlated (ps_001)
with each other and with PAH Mutagenicity variables and PAH were
also significantly (ps_005) correlated with automotive tracers BRF and
PBF For the combined episode as well as day and night data correlations
with BRF were higher than with PBF Mutagenic density and PAH were
also positively correlated with particulate NO and gaseous CO NO3
NO2bull There were significant negative correlations of mutagenic density
with CLF and o 3 PAH were also negatively correlated with Dy
Among the PAH variables COR was very highly correlated (ps_001) with
CO PBF and BRF all three considered primarily automotive pollutants
COR was also correlated with NO and NO and KF In other studies2
KF has been identified as a wood smoke tracer (44) Although not shown
in the tables correlations of BKF were like BAP and BGP like COR
-32-
TABLE ID-3
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
DAYTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
3M398PS9 revm 24 24 14 6 58
M398M59 revm3 24 10 6 2 27
ORG98PS9 revmicrog 23 12 10 ltl 39
ORG98MS9 revmicrog 23 5 5 ltl 8 3M398NRM revm 16 4 2 1 7
NR98M3 16 035 022 012 110
BAP ngm3 24 02 01 01 04
BKF ngm3 24 01 01 01 03
BGP ngm3 24 11 07 02 24
COR ngm3 24 07 04 01 16
BZO ngm3 24 08 06 01 20
ORG microgm 3 23 36 27 15 92
TSP microgm 3 23 76 25 34 139
NO microgm 3 23 86 34 32 1583
so= microgm 3 23 84 44 51 2144
BRF microgm 3 24 50 31 8 114
PBF microgm 3 24 266 157 49 638
BRFPBF 24 019 007 010 042
ZNF ngm3 24 31 24 9 123
KF ngm3 24 157 129 38 491
FEF ngm3 24 144 98 28 371
SIF ngm3 24 326 284 24 1220
CLF ngm3 24 174 282 19 1450
NIF ngm3 24 8 8 2 33
SF ngm3 24 1810 1384 442 7640
co ppm 18 13 04 06 21
NO pphm 21 22 15 05 64
NO2 pphm 23 26 11 12 53
pphm 23 29 15 aa 5903
502 pphm 23 04 09 oo 43
-32a-
TABLE ill- 4
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM SIX EPISODES
NIGHTTIME SAMPLES 1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 24 17 10 ltl 37
M398MS9 revm3 24 9 5 ltl 18
ORG98PS9 rev microg 24 9 6 ltl 21
ORG98MS9 rev microg 24 4 3 ltl 10
M398NRM revm3 16 4 2 l 6
NR98M3 16 036 013 018 070
BAP ngm3 24 02 03 01 15
BKF ngm3 24 01 01 01 05
BGP ngm3 24 08 07 02 28
COR ngm3 24 05 03 01 15
BZO ngm3 24 07 10 01 44
ORG microgm 3 24 33 23 11 88
TSP microgm3 24 52 21 15 109 NO - microgm3 24 71 49 32 205
so= 3
microgm 3 24 86 44 50 2314 3BRF ngm 24 41 30 7 133
PBF ngm3 24 218 168 38 714
BRFPBF 24 021 010 011 041
ZNF ngm3 24 20 11 3 52
KF ngm3 24 127 82 54 377 3FEF ngm 24 112 90 24 353
SIF ngm3 24 256 205 87 787
CLF ngm3 24 346 582 31 2895
NIF ngm3 24 7 7 2 30
SF ngm3 24 1785 1094 590 5305
co ppm 18 10 04 02 17
NO pphm 21 15 13 01 50
NO2 pphm 23 25 12 06 51
03 pphm 23 15 09 01 35
502 pphm 23 03 06 00 25
-32b-
TABLE ill- 5
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLL UT ANTS
COMBINED EPISODE DATA 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 094 045 054 060
TA98-S9 094 100 049 044 059
BAP 045 049 100 038 092
COR middot054 044 037 100 056
BZO 060 059 092 056 100
PBF 028 025 008 071 019
BRF 040 038 030 074 044
KF 026 022 015 058 008
ZNF 012 012 -001 027 026
FEF 009 013 -007 028 -005
SIF -012 001 -007 013 -009
CLF -027 -022 001 -015 -005
NIF -010 -007 -012 -020 -012
SF 022 023 028 003 036
NO3 049 051 032 015 047
co 054 051 023 071 036
NO 051 045 034 049 044
NO2 032 031 011 061 018
03 -027 -035 -041 -013 -043
SO2 004 005 -002 -027 -002
Significant at the p 005 level
Significant at the p 2 001 level
-32c-
TABLE m-6 CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH
AND AIR POLLUTANTS DAYTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 051 050 065
TA98-S9 095 100 057 038 059
BAP 053 057 100 051 077
COR 050 038 051 JI 100 076
BZO 067 059 077 076 100
PBF 019 007 028 070 046
BRF 038 030 059 074 071
KF 024 010 039 066 048
ZNF -014 -019 -019 015 -001
FEF -012 -018 004 019 003
SIF -012 -016 014 015 005
CLF -020 -012 -008 -012 -006
NIF -033 -039 -019 -033 -024
SF 023 028 054 020 045
NO -3 056 057 066 045 064
co 053 042 032 065 054
NO 049 049 046 012 045
NO2 024 012 019 051 026
03 -030 -036 -063 -003 -048
SO2 -003 001 023 -033 000
Significant at the p ~ 005 level
Significant at the p 2- 001 level
-32d-
TABLE ID- 7
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS
NIGHTTIME SAMPLES 1982-1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 095 056 055 066
TA98-S9 095 100 056 050 063
BAP 056 056 100 046 096
COR 055 050 046 100 054
BZO 066 063 096 054 100
PBF 033 035 006 073 013
BRF 043 043 028 077 037
KF 027 033 014 053 018
ZNF 034 047 010 028 015
FEF 021 032 -009 033 -008
SIF 005 016 -012 009 -015
CLF -031 -028 000 -015 -005
NIF 010 019 -012 -013 -007
SF 022 020 026 -008 035
NO3 049 051 030 000 044
co 055 058 028 072 034
NO 051 042 038 071 047
NO2 040 043 010 070 016
03 -050 -047 -041 -050 -053
so2 001 009 -009 -027 -004
Significant at the p _s 005 level
Significant at the p _ 001 level
-32e-
Factor Analysis
Further attempts to characterize major sources of mutagenic air pollution
were carried out using principal component factor analysis Because of
the large number of pollution variables measured interpretation of sources
is difficult The advantage of factor analysis is that it groups the variables
into a smaller number of factors which explain a large portion of the
overall variance in the data set Variables in each factor may have a
common source or formation process (23) Ten aerosol variables were
used including tracers for a variety of sources They were PBF and BRF
(automotive) FEF and SIF (soil) NIF (industry oil refining) CLF (marine
influence) NO (secondary aerosols) SF (industry secondary so =) ZNF3
-4
(many possible sources traffic industry incineration) and KF (possible
agricultural burning or wood smoke indicator) Gas pollutant and meteoroshy
logical results were excluded because of limited or missing data Factor
analysis was not tried using the available meteorological and gas pollutant
data
Approach I Factor Patterns of Major Source Emissions Tracers Excluding
Mutagenic Density and PAH Variables
Consider first the factor patterns obtained without mutagenic density or
PAH variables (Tables III-8-10) Using the ten aerosol source tracers in
the combined episode data set four factors were present which accounted
for 81 percent of the total variance (cf Table Ill-8) The most important
factor (No 1) was heavily loaded with automotive (PBF BRF) and soil
(FEF SIF) tracers and explained 43 percent of the variance KF was
also strongly associated with Factor No 1 The second factor contained
tracers for industry (NIF) as well as soil and explained 16 percent of the
variance The third factor contained tracers for secondary aerosols
(NO - and SF) and explained 12 percent of the variance and the fourth3
factor contained the marine source tracer (CLF) and explained 10 percent
of the variance ZNF was distributed over all four factors implying that
zinc was derived from many sources
-33-
TABLE ill-8
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA 1982-1984 (N = 71)
Factor I Factor 2
PBF (095) NIF (088)
BRF (093) SIF (063)
KF (090) FEF (061)
FEF (0 71) ZNF (042)
SIF (053)
ZNF (048)
Variance Explained () 43 16
Interpretation Automotive Oil Emissions Refining and Soil and Soil
Zinc distributed in all four
Factor 3
SF (084)
N0 - (083)3
ZNF (025)
Factor 4
CLF (096)
ZNF (030)
12
Secondary Aerosols
factors
10
Sea Salt
Sum 81
Factor loadings ~025 are shown in parenthesis
-33a-
TABLE ill- 9
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES 1982-1984 (N = 27)
Factor 1 Factor 2 Factor 3 Factor 4
Variance Explained ()
Interpretation
KF (092)
PBF (090)
FEF (083)
BRF (081)
SIF (080)
NO (028)3
40
Automotive Emissions and Soil
Nitrate found
CLF (094) NIF (087)
ZNF (090) SIF (038)
No - (036) FEF (037)3
18 17
Sea Salt Oil and Zinc Refining
and (some) Soil
in three factors
SF (096)
BRF (038)
NO - (031)3
10 Sum 85
Secondary so=
4Aerosols
Factor loadings 25 are shown in parenthesis
-33b-
TABLE ill- 10
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES 1982-1984 (N = 44)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (095) NIF (081)
PBF (093) SIF (080)
KF (089) FEF (066)
ZNF (0 72) ZNF (034)
FEF (067) KF (027)
SIF (040)
Variance Explained () 48 18
Interpretation Automotive Oil Refining Emissions and Zinc and Soil
Soil
Zinc found in three factors
SF (087)
NO - (087)3
NIF (034)
ZNF (028)
CLF (099)
11
Secondary Aerosols
9
Sea Salt
Sum 86
Factor loadings _025 are shown in parenthesis
-33c-
Both the day and nighttime factor patterns contain the same four factors
with slight modifications (cf Tables III-910) By day the automotive-soil
factor (No 1) explained 40 percent of the variance by night this factor
explained 48 percent of the variance and was also heavily loaded with
ZNF During the day the sea salt (CLF) factor (No 2) contained some
ZNF and explained 18 percent of the variance At night CLF was isolated
in a factor (No 4) which contained only 9 percent of the variance Also
during the day NO3
- -associated aerosols are spread over three factors
(No 1 Auto-soil No 2 Sea salt-zinc No 4 Fine sulphur secondary)
at night NO (secondary aerosol) is found together with fine sulphur3
-
(SF) in factor No 3 This nighttime secondary aerosol factor explained
11 percent of the total variance
Approach II Factor Patterns of Major Source Emissions Tracers Including
Mutagenic Density and PAH Variables
Factor analysis was repeated including one additional mutagenic density
or PAH variable at a time The factor patterns with mutagenic density
coronene and benzanthrone were as follows
i Mutagenic Density
With the addition of mutagenic density (in T A98 +59) to the
combined episode data base five factors were obtained instead of
four (compare Tables III-8 and III-11) Factors loaded with tracers
for auto emissions and soil (No 1) oil refining and soil (No 2)
and sea salt (No 4) were again obtained However with the
mutagenic density variable entered NO was heavily loaded in3
one factor (No 3) while SF was heavily loaded in another (No 5)
Mutagenicity was most strongly associated with the NO - secondary3
aerosol factor (No 3) (loading = 068) and also with the auto-soil
factor (No 1) (loading = 029)
-34-
TABLE ID-11
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (094) NIF (084) NO - (082)3
CLF (094) SF (090)
BRF (093) FEF (060) ZNF (052) ZNF (030) NO - (035)3
KF (090) SIF (060) SF (026) NIF (027)
FEF (0 72) ZNF (050)
SIF (056)
ZNF (037)
Mutagenic (029) (-029) (068) (-041) (008) Density (+S9)
Variance Explained () 39 18 11 10 6 Sum 85
Interpretation Automotive Oil Secondary Sea Second_ary Emissions and Soil
Refining and Soil
(NOtdeg-) and me
Salt (SO -)4
Factor loadings 25 are shown in parenthesis
-34a-
TABLE m-12
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS DAYTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+S9)
Factor 1 Factor 2 Factor 3 Factor 4 Factor 5
PBF (095) CLF (095) NO - (087)3
NIF (086) SF (096)
KF (092) ZNF (091) BRF (031) SIF (053) BRF (030)
BRF (084) NO - (026)3
FEF (052
FEF (075)
SIF (0 71)
Mutagenic (007) (-024) (083) (-024) (013) Density (+59)
Variance Explained () 36 21 16 9 7 Sum 89
Interpretation Automotive Emissions and Soil
Sea Salt and Zinc
Secondary (NO -)
3
Oil Refining
and
Secondary(so =)
4
Soil
Factor loadings ~025 are shown in the parenthesis
-34b-
TABLE ID- 13
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS NIGHTTIME SAMPLES INCLUDING MUTAGENIC DENSITY (+59)
Factor 1 Factor 2 Factor 3 Factor 4
BRF (094) NO - (088)3
PBF (092) SF (085)
KF (089) NIF (032)
ZNF (073) ZNF (028)
FEF (071)
SIF (047)
NIF (081)
SIF (072)
FEF (060)
ZNF (031)
KF (025)
CLF (091)
Mutagenic Density (+S9) (044) (043) (-026) (-059)
Variance Explained () 45 18 11 10 Sum 84
Interpretation Auto Emissions Zinc and
Soil
Secondary Oil Refining and Soil
Sea Salt
Factor loadings 2_)25 are shown in parenthesis
-34c-
Day versus Night comparisons were as follows When mutagenic
density was added to the daytime data set five factors were
obtained (cf Table III-12) However with mutagenicity results in
the nighttime data set only four factors were obtained (cf Table
III-13) In the daytime pattern NO was associated with one3
factor (No3) while SF was associated with another (No 5) In the
nighttime pattern both NO and SF were heavily loaded together3 -
in the same factor (No 2)
The association of mutagenic density with the day and night factor
patterns provides a striking diurnal comparison which invites intershy
pretation During the day mutagenic density was heavily loaded
in the NO factor (No 3) (loading = 083) and not loaded in the3
-
auto-soil factor (No 1) (loading = 007) (cf Table 111-12) However
during the night mutagenic density was loaded equally into the
auto-soil factor (No 1) (loading = 044) and the NO factor (No3
-
2) (loading = 043) We can speculate on the possible significance
of these statistical diurnal differences The strong loading of
mutagenicity in the No --factor during the day suggests that a3
higher percentage of mutagenic aerosols may be associated with
areawide secondary aerosols
The association of mutagenicity with NO --containing aerosols3 especially by day could be the result of aging of primary aerosols
containing mutagens to secondary particulate matter Or it may
be related to nitric acid artifacts known to be present in NO3 measurements made on glass fiber filters As described by Appel
and co-workers (27) a portion of the NO - measured on glass fiber3
filters is due to gaseous HNO3
which binds to reactive (alkaline)
sites on the sampling medium HNO may participate in the3 formation of highly mutagenic nitroarenes either in the air or on
the filters Furthermore HNO exhibits a diurnal pattern with3 maximum values occurring during the day as with o (23) The
3 diurnal behavior of HNO3 may be related to the present finding
-35-
of a strong daytime association between mutagenic density and
NO3- Additional research is required to elucidate these complex
issues For example direct measurement of gaseous HNO3
as well
as aerosol collection with and without a HNO denuder are needed3
In related research Fitz et al (45) compared POM collected on
Hi-Vol samplers equipped with and without a HNO denuder and3 found that mutagenicity did not depend on the reexposure of aerosols
to HNO3 during collection in Los Angeles Concentrations of HNO3 in Contra Costa County are much lower than in Los Angeles
suggesting that gas phase HNO artifacts probably did not signifishy3 cantly influence results of mutagenicity measurements made in the
present study
Finally negative associations were obtained between mutagenic
density and both the sea salt and oil-soil factors Negative
mutagenicity loadings on these factors were found consistently in
the combined episode and day and night data (Tables III-11-13)
The negative association with CLF may reflect directional transport
of pollutants by sea breezes However the explanation for the
negative association of mutagenicity with the oil-soil factor is
not clear
ii Coronene
When the results for coronene were combined with those of ten
aerosol tracer pollutants factor analysis of the combined episode
data base gave the pattern shown in Table III-14 (Similar results
not shown were obtained using either the day or the night data)
In the case of the combined episode data four factors were resolved
which explained 81 percent of the variance Automotive emissions
(PBF BRF) were found primarily in factor No 1 oil (NIF) and soil
(FEF SIF) tracers were in factor No 2 secondary aerosols (NO3-
SF) were in a third and the marine tracer (CLF) in a fourth factor
-36-
TABLE ID- 14
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DAT A INCLUDING CORONENE
Factor 1 Factor 2 Factor 3 Factor 4
BRF (091) NIF (081) SF (084) CLF (097)
PBF (090) FEF (0 78) NO - (083)3
ZNF (030)
KF (082) SIF (0 77) ZNF (026)
ZNF (041) ZNF (046)
SIF (035) KF (037)
PBF (032)
Coronene (089) (-024) (005) (-012)
Variance Explained () 42 15 14 10 Sum Bl
Interpretation Automotive Oil Refining Secondary Sea Salt Emissions and Soil Aerosols
Factor loadings ~025 are shown in parenthesis
-36a-
TABLE ill-15
PRINCIPAL COMPONENT FACTORS FOR PARTICULATE AIR POLLUTANTS COMBINED EPISODE DATA INCLUDING BENZANTHRONE
Factor 1 Factor 2 Factor 3 Factor 4
PBF (095) NO - (082)3
NIF (086) CLF (096)
BRF (091) SF (080) SIF (052) ZNF (032)
KF (090) BRF (027) FEF (051)
FEF (079) ZNF (042)
SIF (062)
ZNF (049)
Benzan throne (028) (069) (-041) (-010)
Variance Explained () 39 19 11 10 Sum 79
Interpretation Auto Secondary Oil Sea Salt Emissions Aerosols Refining and Soil and
Soil
Factor loadings ~25 are shown in parenthesis
-36b-
Coronene was heavily loaded only in factor No 1 the automotive
factor which explained 42 percent of the variance Unlike mutashy
genic density COR was not associated with the secondary aerosol
factor (No 3) As with mutagenic density COR was negatively
associated with factors containing tracers for oil refining and soil
(No 2) and sea salt (No 4)
The results of factor analysis using COR amplify the two-variable
correlations described above (cf Table III-5-7) COR was found to
be strongy associated with elemental tracers for automotive
emissions (PBF BRF) in the combined episode as well as the day
and night data sets Thus COR was derived primarily from mobile
sources during these sampling episodes in Contra Costa county
iii Benzanthrone
The factor pattern including benzanthrone with the ten tracer
variables is shown in Table III-15 Only the results for the combined
episode data base are presented However the factor patterns for
day and night were similar Again four factors were resolved
containing tracers for autos and soil (No 1) secondary aerosols
(No 2) oil refining and soil (No 3) and sea salt (No 4) Benzanshy
throne was associated most strongly with the secondary aerosol
factor (loading = 069) and less strongly with the autornoti ve-soil
factor (loading = 028) BZO was also negatively associated with
the oil-soil and sea salt factors Sea breezes presumably
accounted for the negative association with CLF
The observation that benzanthrone a carbonyl-arene was strongly
associated with the secondary (No -) factor could suggest that3
BZO is formed by atmospheric oxidation of precursor PAH Further
oxidation of benzanthrone may lead to its destruction and lower
concentrations with increasing time and at distances downwind from
a source The association of BZO with the auto emissions factor
(No 1 in Table III-15) suggestsmiddot that this oxidized PAH is also
present in tailpipe emissions
-37-
iv Summary
In summary factor analysis revealed that
1 Mutagenic density was associated with secondary aerosols
(NO -) automotive emissions (PBF BRF) and fine surface3
soil (FEF SIF)
2 Coronene was associated with automotive emissions and fine
surface soil
3 Benzanthrone was associated with secondary aerosols as well
as automotive emissions and fine surface soil
4 Comparing mutagenicity and PAH variables mutagenic
density exhibited a factor pattern more like benzanthrone
and unlike coronene In this respect some mutagens and
BZO both behaved like secondary aerosols
3 Geographic Differences
Summary Statistics
Summary statistics for air pollutants measured at each of the four stations
are shown in Tables 111-16-19 Mutagenic density and specific activity
were highest at Concord (29 revm3 14 rev microg respectively) followed 3by Pittsburg The lowest values observed at Martinez were 14 revm
and 7 rev microg These mean values were higher at all four stations in
comparison with mean values measured during the 1981-82 episode study
The mutagenic density (-59) ratio TA98NRTA98 was highest at Richmond
(045) and at least twenty-five percent lower at the other three stations
(031-034) These ratios suggest that NOz-organics contributed a major
fraction of the mutagenic activity observed in the present study These
-38-
TABLE ill-16
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM RICHMOND DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 18 17 u 4 34
M398MS9 revm3 18 7 5 3 16
ORG98PS9 rev microg 17 8 8 ltl 21
ORG98MS9 revmicrog 17 4 4 ltl 10
M398NRM revm3 12 4 1 3 5
NR98M3 12 045 017 033 069
BAP ngm3 18 02 02 01 05
BKF ngm3 18 01 01 01 03
BGP ngm3 18 10 06 04 18
COR ngm3 18 07 03 03 10
BZO ngm3 18 08 07 02 21
ORG microgm 3 17 35 25 16 73
TSP microgm3 17 57 19 24 70
NO microgm 3 17 78 35 40 118 so=
3 microgm 3 17 108 66 57 222
BRF 4
ngm3 18 42 24 9 66
PBF ngm3 18 209 125 52 407
BRFPBF 18 021 009 013 037
ZNF ngm3 18 28 23 9 68
KF ngm3 18 125 75 50 247
FEF ngm3 18 88 66 26 188
SIF ngm3 18 155 121 56 393
CLF ngm3 18 497 825 44 2172
NIF ngm3 18 7 5 2 15
SF ngm3 18 2506 2032 1074 6473
co ppm 18 12 02 09 14
NO pphm 18 15 10 03 30
NO pphm 18 23 11 lO 392 03 pphm 18 23 11 04 36 so pphm 18 01 02 00 042
-38a-
TABLE ill-17
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM MARTINEZ DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 14 8 3 25
M398MS9 3revm 18 7 4 1 12
ORG98PS9 revmicrog 18 7 6 ltl 16
ORG98MS9 rev microg 18 4 3 ltl 7
M398NRM 3revm 12 3 1 2 4
NR98M3 12 032 010 Ol8 043
BAP 3ngm 18 02 01 01 02
BKF 3ngm 18 01 0 01 01
BGP 3ngm 18 06 03 02 10
COR 3ngm 18 03 02 01 07
BZO 3ngm 18 05 03 02 09
ORG microgm 3 18 33 25 16 70
TSP 3microgm 18 77 29 35 124
No -3
so=4
BRF
microgm 3
microgm 3
3ngm
18
18
18
79
107
45
51
52
28
32
68
12
178
204
101
PBF 3ngm 18 229 193 85 599
BRFPBF 18 023 011 016 041
ZNF 3ngm 18 24 8 16 40
KF ngm3 18 143 123 64 386
FEF 3ngm 18 177 121 38 357
SIF ngm3 18 463 354 120 952
CLF 3ngm 18 235 133 61 449
NIF 3ngm 18 15 7 6 27
SF 3ngm 18 1883 741 846 2915
co ppm
NO pphm 9 31 11 24 43
NO2 pphm 15 26 14 15 49
03 pphm 15 18 11 01 27
so2 pphm 15 14 11 05 34
-38b-
TABLE m-18
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM CONCORD DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 29 13 10 44
M398MS9 3revm 18 13 6 4 21
ORG98PS9 revmicrog 17 14 11 2 30
ORG98MS9 rev microg 17 6 5 ltl 14
M398NRM 3revm 12 5 2 3 7
NR98M3 12 034 018 015 058
BAP 3ngm 18 03 03 01 08
BKF 3ngm 18 02 01 01 04
BGP 3ngm 18 14 09 05 26
COR 3ngm 18 09 04 05 15
BZO 3ngm 18 11 11 02 32
ORG 3microgm 17 39 28 15 84
TSP 3microgm 18 54 12 38 74
NO -3
so=4
BRF
microgm3 3microgm
3ngm
18
18
18
73
61
53
28
14
31
47
50
25
126
89
108
PBF 3ngm 18 287 132 202 542
BRFPBF 18 018 008 013 034
ZNF 3ngm 18 20 9 9 31
KF 3ngm 18 137 102 76 339
FEF 3ngm 18 95 41 58 169
SIF 3ngm 18 209 95 134 387
CLF 3ngm 18 120 135 27 380
NIF 3ngm 18 3 2 2 6
SF 3ngm 18 1364 721 641 2614
co ppm 18 12 04 05 17
NO pphm 18 23 13 03 42
NO 2 pphm 18 31 09 20 45
03 pphm 18 19 09 03 28
so2 pphm 18 00 01 00 01
-38c-
TABLE ill- 19
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM PITTSBURG DURING SIX EPISODES
1982-1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 18 23 9 ll 32
M398MS9 3revm 18 10 5 4 17
ORG98PS9 revmicrog 18 11 6 2 18
ORG98MS9 rev microg 18 5 3 ltl 8
M398NRM 3revm 12 4 2 2 5
NR98M3 12 031 01 OlB 039
SAP 3ngm 18 02 01 01 03
SKF 3ngm 18 01 aa 01 02
BGP 3ngm 18 08 05 03 17
COR 3ngm 18 06 04 02 12
BZO 3ngm 18 07 06 01 14
ORG microgm3 18 33 25 15 68
TSP 3microgm 18 67 18 52 101
NO3
so=4
BRF
3microgm 3microgm
3ngm
18
18
18
84
70
42
50
13
37
45
54
22
182
86
117
PSF 3ngm 18 244 182 109 605
SRFPBF 18 017 006 013 027
ZNF 3ngm 18 30 7 20 37
KF 3ngm 18 162 132 86 429
FEF 3ngm 18 153 88 48 256
SIF 3ngm 18 337 197 150 610
CLF 3ngm 18 188 141 59 393
NIF 3ngm 18 5 2 3 9
SF 3ngm 18 1437 613 516 2145
co ppm 18 09 04 06 17
NO pphm 18 13 10 04 28
NO2 pphm 18 22 10 09 37
03 pphm 18 25 13 01 41
SO2 pphm 18 01 01 00 02
-38d-
ratios also suggest that Richmond the furthest west was exposed least
to aged urban pollutants by the predominantly westerly winds during the
periods of sampling
Individual PAH and total benzene soluble organic (ORG) concentrations
were highest at Concord followed by Richmond PAH and ORG concenshy
trations were significantly lower than measured in 1981-82 For example
the highest mean BAP levels by station were measured at Concord The 3 3concentration of BAP was 03 ngm in the present study and 09 ngm
in the previous study (18)
TSP levels were the highest at Martinez probably because the sampling
site was at ground level (1 m) the other sites were located on the rooftops
of one story buildings Fine fraction soil constituents (FEF SIF) were
also highest at Martinez
Mean NO levels showed little geographic variation ranging from 7 3 3 microgm 3 at Concord to 84 microgm 3 at Pittsburg so4 = varied from 61
3microgm 3 at Concord to 108 microgm at Richmond while fine fraction S
showed the same geographic variations as so4 -
PBF and BRF were both fairly consistent by station The highest mean
PBF was 287 ngm 3 at Concord the lowest was 209 ngm 3 at Richmond 3Mean BRF ranged from 53 ngm at Concord to 42 ngm 3 at Richmond
and Pittsburg NIF was highest (15 ngm 3) at the Martinez site located
adjacent to a petrochemical refinery
CLF was more than four times higher at Richmond (497 microgm 3) than at 3Concord (120 microgm ) The high concentration at Richmond probably
reflects its seaward location It is the most westerly of the four sampling
sites
-39-
2
Among the gaseous pollutants mean NO was highest at Martinez (31
pphm) NO at Concord (32 pphm) and o at Pittsburg (25 pphm) so2 3 was found primarily at Martinez (l4 pphm) Mean SO values at the
2 other three stations were~ 01 pphm so is derived from local sources2 at Martinez (eg petrochemical refining sanitary treatment facilities)
CO levels (not measured at Martinez) were fairly constant at the other
stations
Correlation Analysis
Correlations between mutagenic density PAH and selected particulate
and gaseous pollutants measured at the four stations are presented in
Tables IIl-20-23 (Complete correlation matrices are provided in the
Appendix) Mutagenic density was significantly correlated with NO at3 all four stations and was correlated with BRF at three of the stations
However at Concord mutagenic density was not correlated with either
BRF or PBF despite the fact that mean values of all three variables
(mutagenic density BRF PBF) were the highest there PBF and BRF
were consistently and highly significantly (p~001) correlated with COR
at all stations suggesting further that automotive emissions are significant
sources of COR
The station-by-station comparisons revealed positive associations between
mutagenicity and industrial tracers for the first time Mutagenicity was
positively correlated with petrochemical tracers so and fine fraction2
sulfur at Richmond and Martinez At Pittsburg a highly significant
correlation (p~001) between NIF and both mutagenic density variables
(plusmn_S9) was observed (cf Table Ill-22) NIF was also correlated with each
of the three PAH at Pittsburg These correlations probably reflect
co-transport of fine fraction Ni PAH and mutagens to Pittsburg (typically
a receptor site during the six sampling episodes) from upwind sources to
the west The higher nickel concentrations and the lower correlations
between nickel and mutagenicity at Martinez provide further evidence for
the formation of secondary mutagenic aerosols in the atmosphere
-40-
TABLE ill- 20
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT RICHMOND
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 093 069 o75 087
TA98-S9 093 100 072 056 083
BAP 065 072 100 026 091
COR o75 056 026 100 055
BZO 087 083 091 055 100
PBF 057 036 002 081 030
BRF 080 072 042 080 063
KF 052 031 009 064 015
ZNF 031 020 -003 056 030
FEF 038 018 -009 064 017
SIF 053 027 007 071 030
CLF -029 -024 -011 -018 -023
NIF 029 016 -004 021 012
SF 071 084 072 023 073
NO3 070 069 058 037 069
co 066 050 023 087 044
NO 083 078 067 076 077
NO2 059 040 016 067 036
03 -038 -046 -067 000 -054
502 075 067 0 73 053 078
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-40a-
TABLE ID-21
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT MARTINEZ
TA98+S9 TA98-S9 SAP COR BZO
TA98+S9 100 093 029 -001 049
TA98-S9 093 100 033 016 046
BAP 029 033 100 071 083
COR -001 016 071 100 063
BZO 049 046 083 063 100
PBF 013 033 057 084 046
BRF 033 048 073 085 067
KF 018 035 056 079 047
ZNF 014 034 035 054 023
FEF -003 017 043 077 028
SIF -016 002 036 073 022
CLF -032 -026 -025 -001 -024
NIF 010 012 -023 -019 -034
SF 051 051 004 -003 019
NO~- 063 057 016 -001 047
co NO 055 049 083 052 074
N02 029 051 042 074 033
03 -047 -054 -049 -037 -062
so2
074 059 041 -002 052
Significant at the p s_ 005 level
Significant at the p s_ 001 level
tco not measured
-40b-
TABLE ID-22
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS DURING EPISODES
AT CONCORD
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 096 034 031 046
TA98-S9 096 100 042 017 049
BAP 034 042 100 018 095
COR 0o3l 017 018 100 035
BZO 046 049 095 035 100
PBF -014 -026 -027 070 -015
BRF 009 -005 016 o79 028
KF 005 -009 013 074 020
ZNF -013 -017 -003 -004 005
FEF ooo -011 -036 060 -030
SIF -007 -017 -012 062 -011
CLF -002 001 055 -006 052
NIF -002 -014 019 o77 023
SF -001 -007 041 002 0o46
NO -3
057 055 071 037 082
co 056 053 004 050 015
NO 033 026 021 075 036
NO2 004 004 -026 050 -024
03 -009 -011 -040 -011 -039
502 038 040 040 -008 031
Significant at the p _s 005 level
Significant at the p _s 001 level
-40c-
TABLE m-23
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH ANO AIR POLLUTANTS
AT PITTSBURG
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 100 092 068 063 071
TA98-S9 092 100 075 057 071
BAP 068 075 100 083 085
COR 063 057 083 100 085
BZO 071 071 085 085 100
PBF 046 041 064 082 055
BRF 056 055 073 087 069
KF 049 040 050 076 056
ZNF 020 031 041 038 035
FEF 036 041 041 049 017
SIF 017 018 001 013 -021
CLF -031 -016 -007 -021 -006
NIF 073 064 049 057 056
SF 029 032 025 018 031
NO3 056 061 028 020 053
co 0 71 o 71 072 078 066
NO 059 051 055 056 042
NO2 025 023 059 074 049
03 -033 -050 -039 -012 -046
502 -025 -026 -032 -026 -051
Significant at the p 2 005 level
Significant at the p 2 001 level
-40lt3-
To summarize the correlations by station mutagenic density was correlated
positively with source tracers for automotive secondary and industrial
emissions The strengths of these correlations were different at the four
stations Aerosols collected at Richmond exhibited the strongest associashy
tion between mutagenicity and automotive tracers (PBF BRF) Concord
showed the strongest association between mutagenicity and secondary
aerosols (NO -) while mutagenicity was correlated with petrochemical3 industrial source tracers at Richmond and Martinez (so2 SF) These
geographic differences make physical sense in terms of what we know
about the sampling stations Richmond and Martinez have major refineries
nearby whereas Concord is located in the Diablo Valley a downwind
receptor area
4 Episode Comparisons
Although each sampling episode provided only 12 values (or less due to
missing data) for each pollutant variable comparisons of episodes provide
some information about possible seasonal differences in source patterns
Also qualitative comparisons with prevailing meteorological conditions can
be made
Summary Statistics
Summary statistics for air pollutants from each of the six episodes are
presented in Table Ill-24-29 The highest mean mutagenic density (+59)
was 33 revm3 measured during a cold weather episode (No VI) in 3January 1984 and the lowest was 7 revm during a warm August 1982
episode (No I) However the highest mutagenic specific activity (20
rev microg) was measured during September 1983 (No IV) The lowest ratio
of TA98NRTA98 (030) was also observed then suggesting that nitroarenes
may have contributed to the high specific activity of aerosols collected
in Episode IV
-41-
TABLE ill-24
SUMMARY ST A TISTICS FOR AIR POLLUTANTS FROM EPISODE I 0600 August 23-1800 August 24 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 7 4 3 11
M398MS9 revm3 4 3 1 ltl 4
ORG98PS9 revmicrog 4 12 ltl ltl 17
ORG98MS9 rev microg 4 ltl ltl ltl ltl
M398NRM revm3
NR98M3
BAP ngm3 4 01 0 01 01
BKF ngm3 4 01 0 01 01
BGP ngm3 4 04 01 02 05
COR ngm3 4 04 02 02 05
BZO ngm3 4 03 01 02 04
ORG microgm3 4 58 07 48 64
TSP microgm 3 4 37 11 24 52
NO3 microgm 3 4 41 07 32 47 so - microgm 3 4 64 07 57 724 BRF ngm3 4 19 6 12 24
PBF ngm3 4 148 58 85 202
BRFPBF 4 014 001 013 016
ZNF ngm3 4 24 12 9 37
KF ngm3 4 71 17 50 86
FEF ngm3 4 66 21 39 91
SIF ngm3 4 154 56 91 227
CLF ngm3 4 179 49 132 245
NIF ngm 3 4 6 8 2 18
SF ngm3 4 1671 316 1228 1955
co ppm 3 06 02 05 09
NO pphm 3 05 01 03 06
pphm 4 19 07 10 26NO2 03 pphm 4 25 02 22 27
pphm 4 02 02 00 05SOz
-41a-
TABLE ill- 25
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE II 1800 October 12-0600 October 14 1982
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 24 7 16 32
M398MS9 3revm 4 10 2 8 13
ORG98PS9 rev microg 4 4 3 2 9
ORG98MS9 rev microg 4 2 l l 3
M398NRM 3revm 4 4 l 3 5
NR98M3 4 043 010 036 058
SAP 3ngm 4 02 01 02 03
SKF ngm3 4 01 oo 01 01
SGP 3ngm 4 15 06 09 22
COR ngm3 4 11 03 07 15
SZO 3ngm 4 11 03 08 14
ORG microgm 3 4 74 07 68 84
TSP 3microgm 4 92 26 69 124
NO3 3microgm 4 85 14 75 106
so=4
SRF
microgm3 3ngm
4
4
67
95
11
27
58
56
79
117
PSF 3ngm 4 538 92 407 605
SRFPSF 4 017 003 013 020
ZNF ngm3 4 34 11 18 44
KF 3ngm 4 350 78 247 429
FEF ngm3 4 243 85 169 357
SIF 3ngm 4 512 221 387 843
CLF 3ngm 4 101 96 44 244
NIF 3ngm 4 12 5 6 17
SF ngm3 4 2025 713 1225 2773
co ppm 3 15 01 14 17
NO pphm 3 28 14 14 42
NO2 pphm 4 43 06 37 49
03 pphm 4 24 09 15 35
so2 pphm 4 03 04 00 09
-41b-
TABLE ID-26
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE ID 1800 May 17-0600 May 19 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 13 6 7 19
M398MS9 3revm 4 6 2 4 9
ORG98PS9 revmicrog 4 8 4 5 12
ORG98MS9 rev microg 4 4 1 3 5
M398NRM 3revm
NR98M3
BAP 3ngm 4 01 00 01 02
BKF ngm3 4 01 00 01 01
BGP 3ngm 4 07 02 05 09
COR 3ngm 4 06 01 05 07
BZO 3ngm 4 03 02 01 05
ORG microgm 3 4 17 02 15 20
TSP microgm 3 4 68 18 47 91
NO3 microgm 3 4 67 10 57 80
so -4
BRF
microgm3 3ngm
4
4
71
43
14
9
53
32
83
53
PBF ngm3 4 254 16 236 274
BRFPBF 4 017 005 014 024
ZNF ngm3 4 31 26 9 68
KF 3ngm 4 132 41 76 171
FEF ngm3 4 192 81 101 277
SIF 3ngm 4 486 369 147 952
CLF ngm3 4 698 998 62 2173
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1040 254 746 1360
co ppm 3 10 04 06 13
NO pphm 3 11 06 04 14
NO2 pphm 3 28 02 25 30
03 pphm 3 32 07 28 41
SO2 pphm 3 01 01 00 02
-4ic-
TABLE ill- 27
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE IV 1800 September 12-0600 September 14 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm 4 25 15 9 44
M398MS9 revm 4 12 7 4 21
ORG98PS9 rev microg 3 20 9 12 30
ORG98MS9 revmicro g 3 9 4 6 14
M398NRM revm 4 2 1 2 3
NR98M3 4 030 026 015 069
BAP ngm 4 01 01 01 02
BKF ngm 4 01 00 01 01
BGP ngm 4 05 04 03 11
COR ngm 4 03 03 01 07
BZO ngm 4 03 03 01 07
ORG microgm3 3 16 01 15 17
TSP microgm 3 3 62 13 54 77
NO3- microgm3 3 57 01 57 58
so=4
microgm3 3 63 18 50 84
BRF ngm 4 23 11 9 32
PBF ngm 4 146 67 52 207
BRFPBF 4 016 002 014 018
ZNF ngm 4 18 9 9 28
KF ngm 4 94 29 55 124
FEF ngm 4 124 76 26 188
SIF ngm 4 292 203 56 487
CLF ngm 4 93 90 27 227
NIF ngm 4 10 12 2 27
SF ngm 4 1414 561 641 1902
co ppm 3 11 02 09 13
NO pphm 4 18 10 03 25
NO2 pphm 4 20 12 09 33
03 pphm 4 23 05 16 28
so2 pphm 4 04 06 oo 12
-41d-
TABLE ffi- 28
SUMMARY STATISTICS FOR AIR POLLUTANTS FROM EPISODE V 1800 October 4-0600 October 6 1983
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 3revm 4 21 7middot 14 30
M398MS9 3revm 4 9 4 6 15
ORG98PS9 revmicrog 4 12 4 8 17
ORG98MS9 rev microg 4 6 2 4 8
M398NRM 3revm 4 3 middotl 3 4
NR98M3 4 036 006 029 043
BAP 3ngm 4 02 00 01 02
BKF ngm3 4 01 00 01 02
BGP 3ngm 4 10 04 05 15
COR ngm3 4 06 03 03 09
BZO 3ngm 4 08 02 05 10
ORG microgm3 4 18 02 16 19
TSP 3microgm 4 57 4 54 63
NO3 so -
4 BRF
3microgm
microgm 3
3ngm
4
4
4
65
92
41
14
32
11
47
54
28
77
130
52
PBF ngm3 4 218 79 137 310
BRFPBF 4 021 008 015 033
ZNF ngm3 4 23 5 16 27
KF ngm3 4 91 23 64 120
FEF ngm3 4 97 25 73 120
SIF 3ngm 4 162 46 112 202
CLF ngm 3 4 171 153 43 393
NIF 3ngm 4 6 4 2 12
SF ngm3 4 1097 536 516 1753
co ppm 3 13 05 07 17
NO pphm 4 22 08 11 30
NO2 pphm 4 26 06 22 35
03 pphm 4 26 01 24 27
so2 pphm 4 03 06 aa 11
-41e-
TABLE ill-29
SUMMARY STA TISTICS FOR AIR POLLUTANTS FROM EPISODE VI 1800 January 4-0600 January 6 1984
Standard Minimum Maximum Variable Units N Mean Deviation Value Value
M398PS9 revm3 4 33 8 25 43
M398MS9 3revm 4 16 3 12 19
ORG98PS9 revmicrog 4 1B 3 16 21
ORG98MS9 revmicrog 4 8 l 7 10
M398NRM 3revm 4 5 l 4 7
NR98M3 4 033 001 032 035
BAP 3ngm 4 04 03 02 08
BKF ngm3 4 02 01 01 04
BGP 3ngm 4 15 09 06 26
COR 3ngm 4 07 03 03 11
BZO 3ngm 4 18 11 09 32
ORG microgm 3 4 22 09 16 35
TSP microgm3 4 66 6 58 73
NO3 3microgm 4 150 34 118 18l
so=4
BRF
microgm3 3ngm
4
4
150
52
73
18
85
31
222
67
PBF ngm3 4 150 49 108 202
BRFPBF 4 035 006 028 041
ZNF ngm3 4 23 6 17 31
KF 3ngm 4 114 22 94 145
FEF ngm3 4 47 8 38 58
SIF 3ngm 4 139 17 120 154
CLF ngm3 4 319 45 282 380
NIF 3ngm 4 5 l 3 6
SF ngm3 4 3537 1983 2145 6473
co ppm 3 12 02 10 13
NO pphm 4 27 15 07 43
NO2 pphm 4 19 03 15 23
03 pphm 4 02 01 01 04
so2 pphm 4 10 16 oo 34
-41pound-
Higher concentrations of total benzene soluble organics were noted in
episodes I and II than in episodes III-VI suggesting a downward trend over
time In contrast concentrations of specific PAH varied widely from
episode to episode The highest concentrations of PAH were measured
in the stagnant October (1982) and cold January (1984) episodes while the
lowest PAH concentrations were measured during the warm weather
episodes of August 1982 and September 1983
For many particulate pollutants the highest concentrations occurred during
the October 1982 episode (No II) (Table III-25) This probably reflects
the stagnant conditions which prevailed (See episode description above)
These pollutants included TSP PBF FEF and SIF An exception was SF
which was highest during the January 1984 episode when easterly transport
prevailed
Previous me_asurements in Contra Costa County suggested contributions
to air pollution from wood burning in winter (18) In the present study
the KF e ratio associated with airborne particulate matter was used to
approximate the impact of wood combustion on ambient concentrations
The KFe ratio in soil is approximately 05 in emissions from some
non-wood combustion sources the range of ratios found is 02 to 03
Previously it was shown that the ratio in ambient air containing mostly
particles from wood combustion is gt8 (44) In the present comparison
the KFe ratio ranged from 09 to 16 in five of the six episodes However
during January 1984 the KFe ratio was higher 25 Furthermore the
ratio at night was 30 This suggests that during the winter episode some
of the aerosol was derived from wood combustion although not a major
proportion
Among the gases oxides of nitrogen (NO ) were highest in October 1982 X
(No II) o peaked during May 1983 (No III) and so varied from a low3 2
of 01 pphm in May 1983 to a high of 11 pphm in January 1984 (No
VI)
-42-
--- --- -------
Correlation Analysis
Despite the small number of samples points for each episode two-variable
correlations were used to help define short-term phenomena The results
are shown in Tables III-30-35 Due to the small sample size interpretation
should be limited
There was considerable inconsistency from episode to episode of the
associations between mutagenic density on the one hand ~nd NO3- PBF
and BRF on the other Positive correlations with PB or BRF were very
significant (p lt001) in Episodes I and II not significant (at the p lt005
level) in No III significant in No IV and not significant in Episodes V
and VI Mutagenic density and NO - were significantly correlated only3
in Episode I Correlations were lowest during episodes when the range
of concentrations of the variables was small When the combined six
episode data base was analyzed the range of concentrations were greater
and mutagenicity was significantly correlated with PBF BRF and NO3-
Thus pollution patterns observed during each short-term episode did not
mirror the average pollution pattern observed when the data from six
episodes were combined
Mutagenic density variables (either +S9 or -S9) were correlated with COR
in all episodes except No II Mutagenicity correlations with BAP and
BZO were less frequently observed Note that during episode No III in
May 1983 no positive correlations between mutagenic density and any
other measured pollutant were observed (cf Table 111-32) However CLF
was significantly negatively correlated with mutagenic density (_S9)
Throughout sampling in May the winds were on-shore from the west
Among the gases NO was the best correlated with mutagenic density2 Significant positive correlations with NO were found in four episodes2 (No I II IV and V) This association should be investigated further
Finally CO was correlated with mutagenic density in episodes I (August
1982) and V (October 1984)
-43-
TABLE III-30
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE I
0600 August 23-1800 August 24 1982
TA98+S9 TA98-S9 BAPt COR BZO
TA98+S9 100 090 000 052 033
TA98-S9 090 100 000 066 033
BAP 000 000 000 -aa 000
COR 052 066 000 100 059
BZO 032 033 000 059 100
PBF 097 088 000 056 040
BRF 087 082 000 059 068
KF 029 026 000 -041 -017
ZNF 083 061 000 018 004
FEF 032 003 000 -026 006
SIF 020 -003 000 -037 -010
CLF -032 -043 000 -049 003
NIF -026 -046 000 -049 -029
SF 029 006 000 -053 -038
NO -3 085 085 000 055 017
co 028 017 000 044 001
NO 037 017 OD 055 023
NO2 089 075 000 000 014
03 048 038 000 019 -013
so2 -014 -044 000 -056 -045
Significant at the p _ 005 level
Significant at the p middot 001 level
tAll values lt detection limit (0lngm3)
-43a-
TABLE ill- 31 3CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm ff) SELECTED PAH
AND AIR POLLUTANTS FROM EPISODE 1800 October 12-0600 October 14 1982
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 o71-H- 059 080 084
TA98-S9 071 100 078 053 068
BAP 059 078 100 071 082
COR 080 053 071 100 091
BZO 084 068 082 091 100
PBF 064 085 077 066 o73
BRF 067 084 084 073 080
KF 059 058 062 057 069
ZNF 050 070 037 031 040
FEF 039 075 057 027 043
SIF 013 032 028 015 023
CLF -032 005 -016 -039 -035
NIF -019 016 -024 -046 -040
SF -036 -007 -038 -061 -051
NO -3 050 025 010 020 026
co 082 086 081 080 092
NO 052 046 056 083 070
NO2 039 068 066 053 052
03 -007 -053 -056 -032 -033
so2 -022 -007 -005 -024 -013
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43b-
TABLE ID-32
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm31 SELECTED PAH ANO AIR POLLUTANTS FROM EPISODE rn
1800 May 17-0600 May 19 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 098 -037 046 -024
TA98-S9 098 100 -033 049 -017
BAP -037 -033 100 021 072
COR 046 049 021 100 056
BZO -024 -017 072 056 100
PBF 044 047 028 081 067
BRF 006 004 028 066 058
KF -038 -032 041 004 047
ZNF -003 002 016 041 055
FEF -001 007 062 009 057
SIF -022 -018 070 -017 045
CLF -066 -073 -017 -033 -017
NIF -041 -030 049 010 079
SF -040 -033 070 003 068
NO -3 015 026 040 049 061
co -003 -006 000 070 063
NO 003 006 000 083 070
NO2 040 045 000 073 078
03 019 025 000 -018 -011
so2 034 038 000 020 043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43c-
TABLE ill-33
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3J~ SELECTED PAH AND AIR POLLUTANTS FROM EPISODE 1v 1800 September 12-0600 September 14 1983
TA98+S9 TA98-S9 BAP COR BZO
TA98+59 10 097 061 068 070
TA98-S9 097 100 062 065 074
BAP 061 062 100 086 089
COR 068 065 086 100 080
BZO 070 074 089 BO 100
PBF 068 070 063 041 063
BRF 051 056 048 026 0-52
KF 040 048 006 001 006
ZNF 028 029 -021 -031 -024
FEF 037 041 -006 -019 -002
SIF 025 029 -019 -033 -017
CLF -031 -025 021 -015 -009
NIF -012 -009 -039 -053 -010
SF -054 -048 -056 -0 70 -049
NO -3 033 038 -015 003 014
co 052 054 035 058 045
NO 047 039 000 006 009
NO2 057 060 058 047 082
03 010 013 -045 -030 -035
502 002 006 -029 -042 -002
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43d-
TABLE ill- 34
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH7AND AIR POLLUTANTS FROM EPISODE v 1800 October 4-0600 October 6 1983
TA98+59 TA98-S9 BAP COR BZO
TA98+S9 100 096-H- 062 079-H- 083-H-
TA98-S9 096-H- 100 051 064 070
BAP 062 051 100 061 062
COR 079 064 061 100 094
BZO 083-H- 070 062 094-ll- 100
PBF 050 041 030 062 066
BRF 027 018 025 OSi 056
KF 013 003 016 050 048
ZNF 061 055 021 065 081
FEF -002 -004 006 003 024
SIF -004 -002 009 -002 022
CLF -050 -039 -031 -045 -047
NIF -025 -029 013 -014 004
SF 014 003 009 053 040
NO -3 029 030 -007 005 014
co 081 070 051 083 071
NO 061 054 024 057 065
NO2 o79-H- 081 068 045 054
03 004 006 -040 011 012
so2 -051 -049 -023 -053 -043
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43e-
TABLE ill- 35
CORRELATIONS BETWEEN MUTAGENIC DENSITY (revm3) SELECTED PAH AND AIR POLLUTANTS FROM EPISODE VI
1800 January 4-0600 January 6 1984
TA98+S9 TA98-S9 BAP COR BZO
TA98+S9 100 091 031 085 048
TA98-S9 091-lE- 100 039 081-lE- 050
BAP 031 039 100 D54 096
COR 085-lE- 081 054 100 067
BZO 048 050 096 067 100
PBF 053 040 018 060 025
BRF 036 024 031 046 033
KF 010 -003 022 015 020
ZNF -031 -026 -023 -026 -030
FEF 027 013 -010 026 001
SIF -003 -005 004 003 -001
CLF -034 -048 027 -017 018
NIF -006 -010 -027 -041 -024
SF 004 -000 -006 005 -004
NO -3 -014 -007 -040 -056 -040
co 044 051 021 060 024
NO 003 -001 027 008 020
NO2 040 029 052 050 057
03 053 051 -013 045 001
so2 -032 038 -029 -058 -041
Significant at the p ~ 005 level
Significant at the p ~ 001 level
-43pound-
D Conclusions
An effective strategy to control levels of mutagenic density and PAH in
community aerosols should be guided by an understanding of the primary sources
and secondary transformations which produce the mutagens and PAH Our
analysis has shown that the aerosol variables which are the best predictors of
mutagenic density are No and PBF or BRF Furthermore the predictive value3
-
of NO - is area-wide Thus mutagens in particulate matter behaved like both3
primary automotive emission products and secondary aerosols The diurnal
differences in predictive value of PBF may be the result of meteorological
effects During the daytime ventilation was generally good so contributions of
area-wide secondary pollution were predominant During the nighttime lower
inversions and lighter surface winds presumably unmasked local transportation
sources The association of mutagenicity with NO --containing aerosols could3
also be related to atmospheric (or filter) transformations of mutagens catalyzed
by HNO3
Mutagenic density was also correlated with NO and No2 These
correlations were higher at night than by day especially with NO2 Nitration
reactions of PAH involving NO and NO radical at night have recently been2 3 suggested by Pitts et al (23)
Among the PAH coronene was strongly associated with automotive tracers (PBF
BRF) but not with NO3- Benzanthrone a partially oxidized carbonyl-arene
behaved more like mutagenic density than COR That is BZO was associated
with NO3
- as well as with PBF and BRF
Geographic comparisons revealed differences in associations between automotive
tracers and mutagens at different stations Correlations between mutagenic
density and automotive tracers (PBF and BRF) were highest at Richmond and
Pittsburg and lowest at Concord
A positive correlation between mutagenic density and NIF was observed at
Pittsburg but not at the other three locations It should be noted that Pittsburg
site was generally a receptor site (downwind and to the east of the refineries)
during episode sampling Martinez which is closest to the refineries had the
-44-
highest average nickel concentrations but the lowest average mutagenicity This
suggests that the refinery emissions are not identified with primary mutagenic
aerosol emissi ans but may contribute to secondary mutagenic aerosol concenshy
trations at downwind locations
Mutagenicity was also correlated with S compounds (SF 50 ) at Richmond and2
Martinez both industrial centers Thus sulfur producing sources including some
industries may also contribute to mutagenic aerosols Major industrial sources
of sulfur oxides are refineries in Richmond (Chevron) Martinez (Shell Tosco)
and Benicia (Exxon) and a chemical plant in Rodeo (Union) (28)
-45-
CHAPTER IV
SEASONAL VARIATIONS AND TRENDS IN Tl-pound CONCENTRATIONS OF
MUTAGENS PAH AND STANDARD PARTICULATE POLLUTANTS IN
CONTRA COSTA COMMUNITY AEROSOLS
A Introduction
The results of chronic monitoring studies provide critical baseline information
against which the impact of new or expanding technologies (eg diesel cars
waste-to-energy conversions) can be measured Although intensive sampling is
required for source identification (Chapter III) a chronic monitoring strategy is
essential to identify trends in the levels of toxic air contaminants
In our previous CARS-sponsored project in Contra Costa County (18) large
seasonal variations in PAH concentrations were observed Concentrations were
about five times higher in winter than in spring Qualitatively similar but
smaller seasonal swings were exhibited by mutagenic density total mass lead
and other particulate pollutants We concluded that these seasonal patterns
resulted primarily from meteorological variations not seasonal source differences
However we also suggested that wood smoke from fireplaces during the winter
contributed significantly to PAH but not to mutagenic aerosol concentrations
In the Bay Area seasonal changes in dispersal of pollutants are due to changes
in wind direction from west to east wind speeds and inversion heights Higher
concentrations of particulate pollutants during winter are generally observed
In the previous study we also concluded that annual average mutagenic density
and PAH concentrations in Contra Costa County had not changed significantly
between 1979 and 1982 The present study extends the analysis of seasonal
variations and trends through June 1984 using the same logistical plan (Figure
I-2)
B Experimental Methods
Hi-vol samples were collected every sixth day at Concord Richmond and Pittsburg
and used to prepare composite samples for Ames and PAH testing Locations
-46-
and descriptions of the sites are found in Chapter III above Other particulate
pollutants analyzed in the composites were TSP LEAD so = NO - and ORG4 3
A portion of each filter was composited for PAH and mutagenicity testing
(Prior to compositing filters were stored for up to 2 years at -10degC in the
dark) Separate composites were prepared for each station Filters from each
of the three stations were composited over four-month intervals (July-October
November-February March-June) to give composite samples for analysis These
periods approximate the three meteorological seasons in the San Francisco Bay
air basin and also corresponds with those used in previous studies in Contra
Costa County (618)
In the current project samples collected during the period July 1982-June 1984
were composited for analysis of PAH and mutagenic activity Analysis of these
samples provides a continuous data base of concentrations of specific PAH and
mutagenic activity found in Contra Costa air particulate material collected over
a 60 month period from November 1979 through October 1984 Results of PAH
and mutagenicity measurements in composite samples were compared with other
particulate matter pollutants on a season-by-season and annual basis The PAH
and mutagenicity levels were also compared with those measured previously in
Contra Costa County and elsewhere
Air particulate material for mutagenic and PAH testing was collected on 8 x 10
glass fiber filters (Wh_atman) in standard hi-vol samplers The sampling rate 3 was 55-60 m per hour
Analyses of the standard chemical pollutants measured in the ARB air quality
network were carried out by the BAAQMD and AIHL using the standard methods
TSP is determined gravimetrically Pb by energy dispersive x-ray fluorescence
so = turbidimetrically by SulfaVer NO - by a colorimetric procedure utilizing4 3
NitraVer 6 and NitraVer 3 pillows and ORGANICS by benzene extraction followed
by gravimetric determination (Table 1-2) (2831)
-47-
Compositing for mutagenic and PAH testing was performed by cutting pieces
from each filter combining filter disks and extracting with trisolvent as
described above To measure mutagenicity of composites the standard Ames
Salmonellamammalian microsome test was used as described in Chapter III
Methods for the analysis of selected PAH (BAP BKF BGP COR BZO) employed
HPLC with ultraviolet and fluorescence detection and were also as previously
decribed (18)
C Results and Discussion
All results of composite sample analysis are listed in Appendix IV
Comparison by Station
Mean concentrations for pollutants measured at each station are presented in
Table IV-1 Major station-to-station differences were not apparent for most
variables including mutagenic density Among the PAH there were exceptions
however Concentrations of BAP BGP COR and BZO were about twice as high
at Concord as at Pittsburg Total benzene soluble organics (ORG) and lead
were also the highest at Concord
Over the 60 months of composite sampling Richmond had the highest mutagenic
density (114 revm 3 +S9) and Pittsburg the lowest (100 revm 3 +S9) Mutagenic
densities with metabolic activation (+S9) were about twice those measured without
it (-S9) at all three stations Thus the relative amounts of indirect and
direct-acting mutagens were about the same at all locations Richmond experishy
enced the highest so4
= levels (74 microgm 3) but the lowest NO - pollution levels3
(48 microgm 3) Petrochemical refining probably contributed to the so4
= at
Richmond As noted above refineries located in Richmond are major point
sources of sulfur oxides The largest fraction of sulfur oxides released by burning
fossil fuels is so2
so = is considered a secondary pollutant except from sea4
salt and surface entrainment However a proportion (1-2) of the sulfur oxides
from fossil fuel combustion is released as primary so (46)4
=
Seasonal Variations
The seasonal variations are shown in Table IV-2 The November-February (winter)
season middot had the highest concentrations for all the pollutants measured except
-48-
I
TABLE IV-1
MEAN ANO STANDARD DERNA TIONS IN CONCENTRATIONS OF AIR POLLUTANTS SAMPLED AT THREE CONTRA COST A STA TIONS
NOVEMBER 1979-0CTOBER 1984
Station
Richmond Concord Pittsburg Variable Units N Mean SD Mean SD Mean SD
TA98P 3revm 15 11 (7) 11 (7) 10 (7)
TA98M 3revm 15 6 (3) 6 (3) 6 (4)
TA98NRP 3revm 15 5 (3) 6 (3) 5 (3)
TA98NRM 3revm 15 3 (2) 2 (1) 2 (1)
TA98NRMTA98M 15 042 (022) 040 (030) 043 (034)
SAP 3ngm 15 03 (03) 06 (08) 02 (02)
SKF 3 ng 1m 15 02 (02) 03 (03) 02 (02)
SGP 3ngm 15 15 (13) 21 (21) 11 (10)
COR 3
ngm 15 10 (09) 12 (12) 07 (06)
BZO 3ngm 15 05 (06) 11 (15) 06 (08)
ORG 3microgm 15 37 (15) 51 (39) 34 (16)
MASS (TSP) 3microgm 15 57 (9) 51 (15) 64 (13)
LEAD (Hi Vol) 3microgm 15 027 (012) 034 (018) 023 (010)
NO -3
3microgm 14 48 (24) 60 (25) 66 (29)
so -4
3microgm 14 74 (17) 52 (13) 66 (15)
Data from July-October 1984 missing
SD == Standard Deviation
-48a-
TABLE IV-2
SEASONAL VARIATIONS IN CONTRA COST A AIR POLLUTANT CONCENTRATIONS (THREE STA TION AVERAGES)
NOVEMBER 1979-JUNE 1984
Station
Variable Units N Nov-Feb
Mean SD March-June
Mean so July-Oct
Mean SD
- I
TA98P
TA98M
TA98NRP
TA98NRM
TA98NRMTA98M
BAP
SKF
BGP
COR
BZO
ORG
MASS (TSP)
LEAD (Hi Vol)
N03
so=4
3revm
3revm
3revm
3revm
3ngm
3ngm
3ngm
3ngm
3ngm
3microgm
3microgm
microgm 3
microgm3
3microgm
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
14
7
8
3
053
09
05
35
18
19
69
64
042
86
68
(8)
(4)
(2)
(1)
(033)
(06)
(02)
(15)
(10)
(11)
(25)
(13)
(015)
(22)
(22)
8
5
3
2
039
01
01
06
05
01
24
50
019
36
57
(6)
(3)
(2)
(1)
(027)
(002)
(004)
(03)
(03)
(01)
(09)
(10)
(004)
(08)
(11)
11
5
5
2
033
01
01
07
05)
02
28
58
022
50
68
(5)
(2)
(2)
(1)
(014)
(003)
(003)
(02)
(03)
(01)
(10)
(13)
(10)
(12)
(13)
N=l4 missing July-Oct 1984
SD = Standard Deviation
-48b-
so4- Levels of SO were the same during the July-October and Novembershy
4 -
3February seasons (ie 68 microgm ) and only about twenty percent lower during 3March-June (5 7 micro g m )
Concentrations of mutagenic density Pb NO and ORG were all about twice3
as high in the winter as in the spring (March-June)
In confirmation of earlier results (18) levels of specific PAH showed the largest
seasonal variations The concentration of BAP was 09 ngm 3 in Novembershy
February and lt01 ngm3 during the other two seasons SKF BGP and COR
were all 4-6 times more concentrated in winter while BZO was more than 10
times higher in the winter season The large seasonal changes among the PAH
could result (partially) from differences in source patterns Residential wood
combustion would be expected to contribute more to PAH pollution in the winter
Seasonal variations may also reflect selective losses of PAH in warmer seasons
through chemical tranformations in the atmosphere or through volatilization or
chemical transformations during sampling on filters These are topics for other
studies
With respect to possible atmospheric formation of nitroarenes we note that the
TA98NRTA98 ratio was lower in the warm weather seasons (March-June (039)
and July-October (036)) than in winter (November-February (053)) The lower
the ratio the greater the fraction of mutagenic activity contributed by nitroshy
organics including some NO PAH Regarding TA98NR some caveats should2 be included Strain TA98NR is deficient in the bacterial nitroreductase which
catalyzes the activation of most mononitroarenes (eg 1-nitropyrene) to mutagens
Thus a lower response in TA98NR relative to T A98 probably indicates the
presence of mononitroarenes in the sample However certain highly mutagenic
dinitroarenes (eg 18 dinitropyrene) are activated by a different nitroreductase
which is functional in TA98NR Since dinitropyrenes are highly mutagenic in
both T A98 and TA98NR the ratio of TA98NRTA98 could be high yet the sample
could contain these compounds and be highly mutagenic (Another nitroreducshy
tase-deficient strain TA98l8-DNP6
which lacks the specific nitro reductase
required for dinitropyrene activation can be used to indicate the presence of
dinitropyrenes in samples) (47)
-49-
The observation that higher concentrations of PAH mutagenic density and other
particulate matter pollutants occur in winter is consistent with results of our
earlier study in Contra Costa County (18) Values of mutagenic density are
also comparable to albiet somewhat lower than those measured in urban and
residential areas in Los Angeles (23) and elsewere (1648)
Trends
All data used in the analysis of trends are included in Appendix IV
As described in the following one of the most interesting and puzzling results
of this research is the apparent downward trend in some aerosol pollutant
concentrations and the apparent increasing trend in mutagenic density over time
Despite seasonal variations two standard measures of particulate matter pollution
(Pb N0 -) showed overall downward trends during the period (Figures IV-1-2)3
TSP and so levels were fairly constant (Figures IV-3-4) Similar trends were4
=
reported in our earlier study It is perhaps relevant to note that some of this
study was conducted during some of the wettest years ever recorded in California
On an annual basis PAH (and ORG) concentrations were fairlyen constant over
time the exception was in one unusually high winter season (November 1982-
February 1983) (Figures IV-5-8) The explanation for this one season excursion
was not obviously related to average meteorology during the four months of
sampling (38) November was cooler windier and much wetter than normal
December had nearly normal precipitation and ventilation January was dry and
stagnant in the first half and wet and windy in the second half while Februarys
weather was dominated by rain
Quantitative comparisons of trends in the inorganic and organic aerosol pollutants
described above are shown in Appendix V Linear regression analysis demonstrated
that between 1979 and 1984 statistically significant (plt 005) decreases in Pb
concentrations occurred during the Nov-Feb and July-Oct seasons as well as
-50-
SEASONAL COMPOSITES LEAD AVERAGE OF THREE STATIONS
CI)
~
LI I ()
0 Pl J I
D lt w _J
1 0
09
08
01
o 6
o 5
o 4
o 3
02
o 1
o 0
lt I I-
v lt lt r r -lt lt r r lt L lt r lt lt r lt lt lt v lt lt t r lt r lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt r lt lt NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 BO 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Figure IV-1 Lead Seasonal Composites Average of Three Stations Lead concentrations were measured every sixth day at each of three stations and the results averaged over four month se~sons (July-October NovembershyFebruary March-June)
SEASONAL COMPOSITES NITRATE AVERAGE OF THREE STATIONS
12 0
Figure IV-2
10 0
cw 8 0
~
L) I )
Ul 0 tr I w 6 0
I-lta I-1--4
z 4 0
2 0
at each of three stations and the results averaged four month seasons (July-October November-February March-June)
0 0 I VVVVVLLLVVLVLVL(V(j(V(LLVLLLYLLLYLLJI ---1-NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
Nitrate Seasonal Composites Average of Three Stations Nitrate concentrations were measured every sixth day
oven
1-f
lt I
N
Q) --0 rO
-shy rO gt rO
+J 0 z
SEASONAL COMPOSITES TSP MASS AVERAGE OF THREE STATIONS
90 __
Figure IV-3 TSP Mass Seasonal Composites Average of Three Stations Total suspended particulate mass concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (July-October November-February March-June)
80
70
60 CI)
~
~ ~ so w~~~~~~~ W~4w I~ U1 40 ()
lt ~
30
20
10
0 1 r L pound lt K lt r r r lt r r Lr L lt Lr lt Lr r L r r lt r L L r L lt r lt lt lt r lt lt lt r lt r r lt lt
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
ro micro 0 z
SEASONAL COMPOSITES SULFATE AVERAGE OF THREE STATIONS
120r-------------------------
Figure IV-4 Sulfate Seasonal Composites Average of Three Stations Sulfate concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (Julyshy10 0
1--lt
October November-February March-June)
Cl) 8 0 E
- I J ltu-- I
0 p
fmiddot s aw l-lt LL _J J (f) 4 0
QJ --0 ro --
2 oL VY H N H Y AA A IVVVVV1 -~
O 0 I VLLLVLLLVLLLYLLLYLLLVLLLVLLLVLLLV(V((V(VVEEEV(1 L_ NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES ORGANICS AVERAGE OF THREE STAIONS
120-------------------------
10 0
Cl)
~ 80
L)
I l5 0
middot~(1)
601 ~ I
Figure IV-5 Organics Seasonal Composites Average of Three Stations Benzene soluble organic concentrations were measured every sixth day at each of three stations and the results averaged over four month seasons (JulyshyOctober November-February March-June)
~ ~ I fU1 u z lt L) Ck 4 0 0
2 0
O 0 1 r lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r r lt lt L r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r lt lt r lt lt lt r lt lt lt 1
NOV MAR JUL NOV MAR JUL NOV 79 80 80 NfJ ttfiR 1~L ttflV Mtf J~ Nfl Mb~ iL 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES BENZO(A)PYRENEltBAP) AVERAGE OF THREE STATIONS
5 0
l Figure IV-6 Benzo(a)pyrene Seasonal Composites Average of Three
4 5 Stations BAP concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations
CII Separate station composites were prepared by comshyE 4 0 bining pieces of filters every four months and
(_) extracting Composite values at the three stations z were averaged to obtain the seasonal composite3 5
CL 3 0 lt
I CDu- _0 Hi w lt
II 2 5 0)z w 0 gt- 2 0 CL lt -J 1 50
z w CD
N
ldegr o 5 -
o 0 [ lt C C g C lt C [ C C C g lt lt C g lt c c g lt C lts ltlterltlt erltlt er cc cc cc er cc cs cc er cc er cc c
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
~
L) z
I l5l 0
LO I w z
w z a a u
SEASONAL COMPOSITES CORONENE AVERAGE OF THREE STATIONS
50 I
Figure IV-7 Coronene Seasona1 Composites Average of Three 4 5 - Stations Coronene concentrations were measured in
seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by comshy4 0 bining pieces of filters every four months and extracting Composite values at the three stations were averaged to obtain the seasonal composite
35
3 0 I--lt
lt I
---J2 5
2 0
15
10
o 0 amp r c bull laquo s s bull laquo s laquo r lt laquo r _
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
05
SEASONAL COMPOSITES BENZANTHRONECBO) AVERAGE OF THREE STATIONS
50 _______________________
Figure IV-8 Benzanthrone Seasonal Composites Average of Three Stations Benzanthrone concentrations were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by combining pieces of
4 5
4 0 Cl) filters every four months and extracting Composite
~ values at the three stations were averaged to obtain the
seasonal composite middot tJ 3 5 z
3 0 I D u 0) lt 1 0
~ I CXlw 25
z D n J 2 0 1-z lt 1 5 N z w 0)
1 0
o 5
o 0 r c c r r r laquo r c r c c r c c r c -----
NOV MAR JUL NOV MAR JUL NOV middot MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98-S9) AVERAGE OF THREE STATIONS1s o_______________________________________
Figure IV-9 Mutagenic Density (TA98-S9) Seasonal Composites Average of Three Stations Mutagenic densities (-S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stashytions Separate station composites were prepared by combining pieces of filters every four months and exshy
m E -
tracting Composite values at the three stations averaged to obtain the seasonal composite
were
gt w 10 0 ~
I lJ1 0 I-middot I
-_ 0) U)
I--lt
lt I
lD
I CD 01 lt I- lt I-
50
J ~
O 0 1 y r pound r NOV MAR
r lt r lt pound
JUL L r pound
NOV lt L r -lt
MAR r lt r lt lt lt r lt lt lt r lt lt lt r lt lt lt r c lt lt r lt lt
JUL NOV MAR JUL NOV MAR lt r JUL
lt lt r lt lt lt r lt
NOV MAR L lt r lt
JUL lt lt
NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
SEASONAL COMPOSITES MUTAltTA98+S9) AVERAGE OF THREE STATIONS
300-------------------------
25 0
Figure IV-10 Mutagenic Density (TA98+S9) Seasonal Composites Average of Three Stations Mutagenic densities (+S9) were measured in seasonal composite extracts prepared from hi-vol filters collected every sixth day at three stations Separate station composites were prepared by
m ~
combining pieces of filters every four months and extracting Composite values at the three stations
averaged to obtain the seasonal composite were
gt w 200 0
I 1--1 Ul 0 u
I
r- 0) () 15 0
lt I
0
+ CD 0) lt I- lt 10 0 I-J E
5 0
o 0 I 5 C C lt I C C C I C lt lt I lt lt C I C C C I lt lt C I C C lt I pound C C P lt C C [ C C C J C lt C [ C pound C I C C lt I C C L S C lt lt I
NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV MAR JUL NOV 79 80 80 80 81 81 81 82 82 82 83 83 83 84 84 84
COMPOSITE PERIOD
MUTA TRENDS FOR NOV-FEB Figure IV-11AVERAGE OF THREE STATIONS Mutagenic Density Trends for Nov-Feb Average300----~--------of Three Stations Trends in mutagenic density for the five winter seasons 1979-1984 are comshypared by linear regression analyss For TA98+S9 r=085 and b(slope)= 40 revyr bull For TA98-S9 r=079 and b=l9 revyr
250 cq
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=5 a=-79199920 s=2885 1608I gt-
lJ1 0 6=40030 s1t=l 4557 X I--lts11=4 6033 r=08461 ltI (f) I15 0 f--z
f--w A D MUTAC-S9)
SYMBOL=Au bull1-1 LINETYPE= middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bx10 0 w bull n=5 ~ a=-38377400 e=16971295lt b=l 9400 eb=0 8563 J I-
A A A e_11=2 7078 r=0 7944
~ 50
00a--bull----------------------------------1978 1979 1980 1981 1982 1983 1984
YEAR
MUTA TRENDS FOR MARCH-JUNE AVERAGE OF THREE STATIONS
300-------------------~-- Figure IV-12 Mutagenic Density Trends for March-June Average of Three Stations Trends in mutagenic density for the five spring seasons 1979-1984 are compared by linear regression analysis For
250 TA98+S9- r=095 and b(slope) = 39 revyr For CIJ TA98-S9 r=091 and b = 19 revyr
gt E MUTAC+S9)
SYMBOL=bull QJ LINETYPE=--shyL 200 y=a+bx
n=S a=-7781 7600 a=1492 4784middot I-lt
I gt-Ul I- b=39300 ea=0 7530 lt 0 1--t-tI- Ne_=2 3812 r-=09491
l
I (J) 150z
LlJ D MUTAC-S9)
SYMBOL=Au LINETYPE=middot middot middot middot middot middot middot middotmiddot middot middot middot t-t A y=a+bxz 10 0
LlJ n=5 lt ~ a=-38422800 e=981 2984
b=l9410 e11=0 4951I-) e_=1 5657 r-=09147E
-
5 0
a middotmiddotmiddotbull 001------1---=----1L---L--_j_____j____L__ _j
1978 1979 1980 1981 1982 1983 1984
YEAR
- middotAmiddotmiddotmiddot A
MUTA TRENDS FOR JULY-OCTOBER Figure IV-13AVERAGE OF THREE STATIONS
300 _______________ Mutagenic Density Trends for July-Oct Average of Three Stations Trends in mutagenic density for the five summer seasons 1979-1984 are compared by linear regression analysis For TA98+S9 r=083 and b(slope)= 20 revyr For TA98-S9 r=095 and b=l1 revyr250
(lJ
gt e MUTA(+S9)
SYMBOL=bull QJ LINETYPE=-shyL 2~t0 y=a+bbullx
n=5 1---ia=-39846460 e=1541 0467I gt-
~ I- I6=20160 ebull=0 7775 lt 0 I--1--t 8-x=2 4587 r=08315 w~ Cf)
15 0 z w D MUTA(-S9)
SYMBOL=Au 1--t LINETYPE=middot middot middot middot middot middot middot middot middot middot middot middot z y=a+bbullx10 0 w M=5() a=-21867120 e=435 3248lt b=l1060 e11=0 2196I-J ex=0 6946 r=09456 ~
bull
bull bull
A A bull bull bull bull bull bull bull bull ~ 5 0
A middotmiddotmiddotbullA A middotmiddotbull
00-------------------------------------
1978 1979 1980 1981 1982 1983 1984
YEAR
bullbull
TREND FOR TA98NRTA98 CONTRA COSTA COMPOSITE DATA 1979-1984
1 0
Figure IV-14 Seasonal Composite Trends for TA98NRTA98 Average of Three Stations Five year trends in the mutagenic density ratio TA98NR(-S9)TA98(-S9) are compared by season
~
middot-~- -~-- ~ - - middot _ - _ _ OV-FEB- -middot-- middot --bull
~ -~ - - JUL-OCT middotmiddotmiddotbull
MAR-JUN
I V1 0
~
00 0) lt f--~ z 00 0) ltf-
o 9
o 8
07
o 6 r-
o 5
o 4
o 3
o 2
o 1
o 0 1979 1980 1981 1982 1983 1984
YEAR
lt I
--- ~
TABLE IV-3
COMPOSITE MUT AGENICITY TREND DAT A
STRATIFIED BY LOCATION
Mean Mutagenic Density in TA98+S9 by Year (3-Season Average) 1980 1981 1982 1983 1984
I Location Mean SD Mean SD Mean SD Mean SD Mean so lJl 0 0 I
Pittsburg 36 (22) 52 (35) 101 (49) 114 (34) 195 (93)
Richmond 66 (50) 114 (84) 69 (41) 136 (20) 187 (82)
Concord 45 (31) 81 (60) 97 (64) 145 (34) 188 (140)
3-Station Average 49 (34) 82 (61) 89 (48) 131 (29) 190 (65)
SD= Standard Deviation
TABLE IV-4
COMPOSITE MUTAGENICITY DATA STRATIFIED BY SEASON AND LOCATION
Mutagenic Density (TA98+S9) By Year Season Location 1980 1981 1982 1983 1984
Nov-Feb Pittsburg 54 88 132 113 301 Richmond 123 127 113 147 274 Concord 48 144 55 148 226
Three Station Average 75 120 100 136 267 so (42) (29) (40) (20) (38)
Mar-June Pittsburg 11 18 45 81 161 Richmond 34 24 60 113 175 Concord 12 24 66 110 192
Three Station Average 19 22 57 101 176 so (13) (03) (11) (18) (16)
July-Oct Pittsburg 44 51 127 148 124 Richmond 40 191 33 147 111 Concord 74 74 171 178 147
Three Station Average 53 105 110 158 127 so (19) (75) (70) (18) (18)
SD = Standard Deviation
-Sop-
TABLE IV-5
LINEAR REGRESSION ANALYSIS OF COMPOSITE MUTAGENICITY DAT A (MUT AGENIC DENSITY IN TA98 + 59)
YEAR VERSUS LOCATION AND SEASON
TA98 + 59 Versus
R2Location Slope (rev yr) F Probability
bull Pittsburg
bull Richmond
092
069
38
26
36
7
0009
008
bull Concord 098 35 134 0001
TA98 + S9 Versus Season
bull Nov-Feb 072 40 8 007
bull March-June 090 39 27 001
bull July-Oct 069 20 7 008
Three Station (and Season) Average
093 33 41 0008
-50q-
on an annual basis For NO3- a statistically significant decrease also occurred
but only during the Nov-Feb season and on an annual basis No other statistically
significant changes were observed
In contrast to the downward trends in some standard aerosol pollutants (Pb
NO -) and the relative constancy of TSP so and PAH (on an annual basis)4
= 3
mutagenic density exhibited an increasing trend over time (Figures IV-9-10)
Concentrations of both direct-acting (-S9) and indirect-acting (+S9) mutagens
increased over the study period especially during the two seasons November
1983-June 1984 For example during the five winter seasons -59 values increased
from 4 to 14-revm3 and +S9 values from 75 to 27 revm3 (cf Figure IV-11)
Similar trends in mutagenicity were observed during the spring (Figure IV-12)
and summer (Figure IV-13)
The trend in mutagenicity can be analyzed in more detail by stratifying the
composite data by location and season Table IV-3 lists the (3-season average)
mutagenic density (+59) by location for the different years of the study
Qualitatively it is clear the increase in mutagenicity occurred at all three Contra
Costa locations Table IV-4 lists the mutagenic density (+S9) at each location
by season for each year of the study A nine-fold increase (from 2 to 18 3revertantsm ) occurred during the spring season a 2-3 fold increase (from 5
to 13 revertantsm 3) occurred during the summer and a 3-4 fold increase (from 375 to 27 revm ) in the winter as noted above
To provide further comparisons linear regression analysis was carried out relating
mutagenic density (+S9) with time both by station and by season The results
of linear regression analysis are listed in Table IV-5 The highest correlation 2between mutagenicity and time was at Concord (R = 098) and the lowest at
Richmond (R2 = 0 70) Thus the trend is most uniform at Concord a non-indust~ial
location and least uniform at Richmond an industrial location most subject to
marine influences Concerning the seasonal time trends the highest correlation
occurred in the spring (R2 = 090) when meteorlogical conditions are most 2 2uniform and the lowest in the summer (R = 069) and winter (R = 072) when
meteorological conditions are more variable
-51-
Increasing mutagenic density may reflect larger contributions from NOz-PAH
The possibility of an increasing impact over time of NO -PAH is suggested by2
a decreasing trend in the ratio of TA98NRTA98 (Figure IV-14) This decrease
suggests that NO -PAH are becoming more prominent contributors to the observed2
mutagenic density Combustion related emissions are well known primary sources
of nitroarenes which may also be produced by secondary atmospheric reactions
The increase in mutagenic density may also be due in part to lower rainfall in
the Bay Area during the first half of 1984 However it is not obvious how this
could lead specifically to higher pollution levels of mutagenic aerosols and not
other aerosol pollutants
Regarding the trends in mutagenic density described above some statements as
to the consistency and quality control of filters sample handling procedures
storage and mutagenic testing controls should be made The first issue conshy
founding the trend analysis concerns the filters used to collect the air particulate
matter Composites for Ames testing were prepared from particles collected
on glass fiber filters used during routine monitoring by the Bay Area Air Quality
Management District The filters were purchased under EPA specification Of
possible relevance to the trend analysis is the fact that the filters actually used
until December 1982 were Schleicher and Schwell f1-HV (SampS) while since
January 1983 Whatman EPM 2000 hi-vol filters have been used These two
filters have large variations in alkalinity (49) which could amplify the artifact
problem As described earlier gas phase HNO can bind to alkaline sites on3 glass fiber and bound HNO3 may catalyze chemical transformations of PAH to
produce highly mutagenic nitroaromatic compounds during sampling collection
The available alkalinities varied by about a factor of two from 73 micro equivg
for Whatman to 143 micro equivg for SampS filters (49) Fluctuations of this magnitude
make attempts at trend analysis difficult Nevertheless it should be noted that
the expected impact of changing from higher pH SampS to lower pH Whatman
filters is to decrease the potential for HNO -binding3
Following collections of filters by BAAQMD staff the filters were transported
to AIHL Because of logistical and resource limitations the time interval
-52-
between filter collection and delivery to the lab was typically 3-4 weeks during
which time the filters were held at room temperature Once in the lab within
several days pieces of filters for compositing were cut out and stored at -10degC
in glassine envelopes wrapped in aluminum foil inside of zip-lock plastic bags
The time of cold storage of composite filters in this manner varied from several
months to more than two years No appropriate data for investigating the
relationship between storage time and mutagenicity are available Also replicate
analysis of filters from the same composite was not performed so the variability
in the extraction and mutagenic assay of composites could not be assessed
However an estimate of the experiment-to-experiment variability in the Ames
assay itself can be obtained by comparing the variations in responses of positive
control mutagens which were tested in parallel with the composites The three
positive controls used and their respective coefficients of variation over the
study period were 2-aminofluorene 28 2-nitrofluorene 30 and 4-nitroshy
quinoline-N-oxide 30 Based on these quality control data we cannot rule
out the possibility that methodological factors may explain the positive trend
in mutagenic density
Although detailed analysis of weather patterns over the study period is beyond
the scope of this report the following observations may provide some insight
into the origins of the apparent increase in mutagenic density (Sandberg J
personal communication) The use of weather factors to adjust trend studies
has proved useful with ozone and of some value with carbon monoxide but of
limited value for particulate matter The 24-hour basis of particulate measureshy
ments and the strong diurnal patterns (including wind direction reversals) typically
observed in a 24-hour period in our complex terrain have made it difficult to
isolate the weather factors most relevant for TSP on different types of days
over the course of a year or series of years However the weather factors
for ozone may be relevant for the photochemically related nitrate compounds
(and nitroarenes) 1982 was a cool clean year and 1983 and 1984 were very
warm years with weaker than normal sea-breeze penetration related to the global
El Nino event Consequently days over the Federal ozone standard did increase
by a factor of four-from 5 in 1982 to 21 in 1983 and 22 in 1984 The ozone
season is an extended summer event but 1984 was particularly noteworthy for
-53-
its early ozone season with mid-summer weather conditions observed in mid-April
and in May These months are classed in our analytic scheme with spring which
is normally cool windy and clean Also the January and February weather
factors for 1984 were atypically warm and dry
Finally we speculate that the actual changes in diesel emissions (50) which took
place over the study period in Contra Costa County especially in the vicinity
of the sampling sites probably did not account for a major proportion of the
increase in mutagenic density Detailed inventories of diesel emissions in the
vicinity of the Contra Costa County sampling stations are being updated and
prepared The overall District diesel emissions do not rise sharply over the
sampling period but the expansion of the bus system in Contra Costa is being
analyzed by BAAQMO staff for local impact
D Conclusions
The following conclusions may be drawn from the results of composite filter
sampling carried out between November 1979-October 1984
1 Seasonal comparisons indicate that higher values of mutagenic density
Pb NO3
- and especially PAH were consistently observed in the winter
seasons (November-February)
2 Decreasing (annual) trends in concentrations of Pb and NO3- were also
measured
3 An increasing trend in the mutagenic density of Contra Costa aerosols
was observed The mutagenic density (revm3) of Contra Costa community
aerosols is three to four times higher in 1984 than it was in 1979 Further
monitoring is needed to determine the persistence of this trend Changes
of this magnitude in pollution concentrations frequently can be explained
by changes in wind direction andor velocity This is particularly true
with small sample sizes Perhaps this is also true for levels of
mutageni city
-54-
In conclusion we emphasize that in evaluating trends in air quality analysts
make one or both of two common assumptions
a Pollutant emissions are constant hence the variations in pollutant
concentrations are the result of some aspect of meteorological
conditions
b Meteorological conditions while not constant are effectively
smoothed out when analyzing long term (ie several years) of data
Since neither these assumptions is strictly valid it is virtually impossible to
establish true trends in pollutant concentrations or its corollary the effectiveness
of control strategies unless the function relationship between concentrations
and meteorology has been determined and this we have not done Only then
will it be possible to utilize historical data for the determination of the true
effectiveness of control strategies
-55-
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2 Talcott R Wei E (1977) Airborne mutagens bioassayed in Salmonella
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8 State of California Air Resources Board A California Ambient Air Quality
Standard for Particulate Matter (PM ) Appendix 4 December 198210
9 National Academy of Science (1972) Particulate polycyclic organic matter
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10 Gordon R Bryan R Rhim J Demoise C Wolford R Freeman A Heubner R
(1973) Transformation of rat and mouse embryo cells by a new class of
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12233-232
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11 Pitts J Formation and fate of gaseous and particulate mutagens and carcinogens
in real and simulated atmospheres (1983) Environ Health Perspec 47115-140
12 Ames B McCann J Yamasaki E (1975) Methods for detecting carcinogens and
mutagens with the Salmonellamammalian-microsome mutagenicity test Mutation
Res 31 347-364
13 Pitts J VanCauwenberge K Grosjean D Schmid J Fitz D Belser W Knudson S
Hynds P Atmospheric reactions of polycyclic aromatic hydrocarbons Facile
formation of mutagenic nitro derivatives (1978) Science 202515-519
14 Schuetzle D Perez J Factors incluencing the emissions of nitrated-polynuclear
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755
15 Wang Y Lee M-S King C Warner P (1980) Evidence for nitro aromatics as
direct-acting mutagens of airborne particulates Chemosphere 983-87
16 Siak J Chan T Gibson T Wolf G (1984) Contribution to bacterial mutagenicity
from nitro-PAH compounds in ambient aerosols paper 84-17 presented at the
77th Annual Meeting Air Pollution Control Association San Francisco June
1984
17 Pitts JN Jr Lokensgard OM Fitz DR (1982b) Chemical nature of particulate
atmospheric mutagens in Californias south coast air basin Final Report
California Air Resources Board Contract No AO-139-32
18 Flessel P Guirguis G Cheng J Chang K Hahn E Chan R Ondo J Fenske R
Twiss S Vance W Wesolowski J Kado N (1984) Monitoring of Mutagens and
Carcinogens in Community Air Final Report California Air Resources Board
Contract No Al-029-32
19 Kado NY Langley D Eisenstadt E (1983) A simple modification of the
Salmonella liquid incubation assay increased sensitivity for detecting mutagens
in human urine Mutation Res 12125-32
-57-
20 Gorse R Riley F Ferris F Pero A Skerves L (1983) lNitropyrene concentrations
and bacterial mutagenicity in on-road vehicle particulate emissions Environ
Sci Technol 17198-202
21 Gibson T (1982) Nitro derivatives of polynuclear aromatic hydrocarbons in
airborne and source particulate matter Atmos Environ 162037-2040
22 Sweetman J Harger W Fitz D Paur HR Winer A Pitts J (1984) Diurnal
mutagenicity of airborne particulate organic matter adjacent to a heavily traveled
West Los Angeles freeway paper 84-165 presented at the 77th Annual Meeting
Air Pollution Control Association San Francisco June 1984
23 Pitts J Winer A Sweetman J et al (1984) Particulate and Gas Phase Mutagens
in Ambient and Simulated Atmospheres Final Report California Air Resources
Board Contract No A3-049-32
24 Shepson P Kleindierst T Edney E Namie G Pittman J Cupitt L Claxton L
(1985) The Mutagenic Activity of Irradiated TolueneNOxH OAir Mixtures2 Environ Sci Tecnol 19249-255
25 Albrechcinski T Michalovic J Gibson T (1984) Atmospheric reactions of
polynuclear aromatic compounds as measured in a smog chamber In Polynuclear
Aromatic Hydrocarbons edited by M Cooke and A Dennis Battelle (in press)
26 Siak J Chan T Gibson T Wolff G (1985) Contribution to Bacterial Mutagenici ty
from Nitro-PAH Compounds in Ambient Aerosols Atmos Environ 19369-376
27 Appel B Tokiwa Y Haik M Kothny E (1984) Artifact Particulate Sulfate and
Nitrate Formation on Filter Media Atmos Environ 18 409-416
28 Bay Area Air Quality Management District Air Quality Handbook 1983-84 (1984)
Bay Area Air Quality Management District San Francisco CA
29 Pitts JN Jr Harger W Lokensgard OM Fitz DR Scorziell GM Mejia V (1982a)
Diurnal variations in the mutagenicity of airborne particulate organic matter in
Californias south coast air basin Mutation Res 10435-41
-58-
30 Grosjean D (1983) Polycyclic aromatic hydrocarbons in Los Angeles air from
samples collected on teflon glass and quart filters Atmospheric Environment
172565-2573
31 US EPA (1981) Quality Assurance Handbook for Air Pollution Measurement
Systems Vol II Ambient Air Specific Methods Revision No 3 EPA-6004-77-
027a
32 Loo BW Adachi RS Cork CP Goulding FS Jaklevic JM Landis DA Searles WL
(1979) A second generation dichotomous sampler for larger-scale monitoring
of airborne particulate matter LBL-8725 Presented at the 86th annual meeting
of the American Institute of Chemical Engineers Houston Texas
33 Flessel P Wesolowski J Twiss S Cheng J Ondo J Manto N Chan R (1982)
The integration of the Ames bioassay and chemical analyses in an epidemiological
cancer incidence study In Second Symposium on Application of Short-term
Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures
(Waters M ed) New York Plenum Press pp 61-84
34 California Department of Health Services (1973) Determination of particulate
lead Method 41 Air and Industrial Hygiene Laboratory Berkeley CA
35 McCann J Springarn NE Kobori J Ames BN (1975) Detection of carcinogens
as mutagens bacterial tester strains with R factor plasmids Proc Natl Acad
Sci (USA) 72979-983
36 Rosenkranz HS Speck WT (1976) Activation of nitrofurantoin to a mutagen
by rat liver nitroreductase Biochem Pharmacol 251555-1556
37 Lowry OH Rosenbrough JN Fan A Randall RJ (1951) Protein measurement
with folin phenol reagent J Biol Chem 193265-275
38 Rosenkranz HS Mermelstein R (1983) Mutagenicity and genotoxicity of
nitroarenes All nitro-containing chemicals were not created equal Mutation
Res 114217-267
-59-
39 Flessel CP Guirguis GN Cheng JC Chang K Hahn ES Twiss S Wesolowski JJ
(1985) Sources of mutagens in Contra Costa County community aerosols during
pollution episodes diurnal variations and relations to source emissions tracers
Environ Internatl (in press)
40 Talcott R Harger W (1980) Airborne mutagens extracted from particles of
respirable size Mutation Res 79177-180
41 Sorenson WG Whang W Simpson JP Hearl FJ Ong T (1982) Studies of the
mutagenic response of Salmonella typhimurium T A98 to size-fractionated air
particles comparison of the fluctuation and plate incorporation tests Environ
Mut 4531-541
42 Giaque R Goulding F Jaklevic J Pehl R (1972) Trace element analysis with
semiconductor detector x-ray spectrometers LBL report-647 Technical Informashy
tion Division Lawrence Berkeley Laboratory
43 Statistical Analysis System Users Guide (1979) Helwig J and Council K eds
SAS Institute Inc Box 8000 Cary North Carolina 27511
44 Sexton K Liu K Hayward S Spengler J (1985) Characterization and source
Apportionment of Wintertime Aerosol in a Wood-Burning Community Atmosph
Environ (in press)
45 Fitz D Lokensgard D Doyle G (1984) Investigation of Filtration Artifacts
When Sampling Ambient Particulate Matter for Mutagen Assay Atmosph
Environ 18205-213
46 Appel B Wau S Wesolowski J (1976) The Chemistry Dispersion and Transport
of Air Pollutants emitted from Fossil Fuel Power Plants in California Final
Report California Air Resources Board Research Contract No ARB 3-948
47 Rosenkranz E McCoy E Mermelstein R Rosenkranz H (1982) Evidence for
Existence of Distinct Nitroreductases in Salmonella typhimurium Roles in
Mutagenesis Carcinogenesis l= 121-123
-60-
48 Takeda N Teranishi K Hamada K (1984) Mutagenicity of air pollutants
collected at industrial urban-residential and rural areas Bull Environ Contamin
Toxicol 32 688-692
49 Witz S Smith M Moore A (1983) = Comparative Performance of Glass Fiber
Hi-Vol Filters J Air Poll Control Assn 33988-991
50 Wei E Wang Y Rappaport S Diesel emissions and the Ames test A
Commentary (1980) J Air Pollut Control Assoc 30267-271
-61-
APPENDICES
APPENDIX I
APPENDIX II
APPENDIX III
APPENDIX IV
APPENDIX V
Wind Speed and Direction at the Mountain View Sewage
Treatment Plant Martinez During Six Sampling Episodes
(1982-1984)
San Francisco Bay Area Weather Factors During Six Sampling
Episodes (1982-1984)
Complete Correlation Matrices for Combined Episodes Dayshy
time and Nighttime Samples and the Four Stations
Complete Data Set for Contra Costa Seasonal Composites
Nov 1979-0ct 1984
Linear Regression Slopes of Composite Aerosol Pollutant
Data 1979-1984 Year versus Season and Annual Average
-62-
APPENDIX I
WINDSPEED and DIRECTION MOUNTAIN VIEW SEWAGE TREATMENT
DURING SIX SAMPLING EPISODES
DATE 82382
PST DRCTN SPEED(m[h) PST
0300 285
0400 285
0500 285
0600 270
0700 270
0800 285
0900 285
1000 285
1100 285
1200 285
1300 300
1400 270
1500 270
1600 270
1700 270
1800 270
1900 255
2000 255
2100 285
2200 285
2300 270
2400 255
12
11
10
8
7
10
12
14
12
12
12
12
12
12
10
9
8
7
6
8
9
9
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
at the PLANT MARTINEZ (1982 - 1984)
82482
DRCTN SPEED(m[h)
255 9
240 7
240 8
240 8
240 7
240 8
240 7
255 7
270 11
270 13
270 14
285 13
285 13
285 12
270 11
255 10
255 9
270 10
270 9
240 7
210 3
270 6
240 2
60 1
APPENDIX I (continued)
DATE 101282 101382 101482
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 195 2 0100 225 2
0200 195 2 0200 225 2
0300 240 3 0300 270 4
0400 255 3 0400 270 4
0500 240 3 0500 285 4
0600 VRBL 1 0600 285 6
0700 VRBL 1 0700 285 8
0800 VRBL 1 0800 285 9
0900 VRBL 1 0900 285 10
1000 60 5 1000 285 10
1100 45 6 1100 285 10
1200 30 4 1200 285 10
1300 30 6 1300 285 9
1400 30 8
1500 30 10 1500 45 5
1600 45 8 1600 45 3
1700 45 6 1700 345 2
1800 60 2 1800 255 1
1900 VRBL 1 1900 225 3
2000 210 1 2000 270 3
2100 VRBL 1 2100 270 6
2200 VRBL 1 2200 285 3
2300 210 1 2300 255 3
2400 VRBL 1 2400 240 1
APPENDIX I (continued)
DATE 51783 51883 51983
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 255 4 0100 VRBL 1
0200 255 4 02JO 210 1
0300 255 3 0300 150 1
0400 240 2 0400 195 2
0500 195 1 0500 VRBL 1
0600 VRBL 1 0600 210 2
0700 240 2 0700 VRBl 1
0800 240 3 0800 VRBL 1
0900 270 5 0900 VRBL 1
1000 300 5 1000 VRBL 2
1100 300 4 1100 030 8
1200 315 5 1200 030 9
1300 300 3 1300 030 10
1400 300 5 1400 030 10
1500 300 5 1500 030 8
1600 360 5 1600 300 6 1600 030 6
1700 300 7 1700 300 6 1700 030 6
1800 285 8 1800 285 4 1800 330 2
1900 285 7 1900 285 5 1900 300 5
2000 270 3 2000 285 6 2000 285 6
2100 VRBL 1 2100 270 6 2100 285 6
2200 VRBL 1 2200 270 5 2200 225 3
2300 VRBL 1 2300 270 3 2300 210 1
2400 255 4 2400 VRBL 1 2400 VRBL 1
APPENDIX I (continued)
DATE 91283 91383 91483
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 240 2 0100 270 5
0200 VRBL 1 0200 270 6
0300 VRBL ltl 0300 270 6
0400 255 1 0400 270 5
0500 270 2 0500 270 7
0600 VRBL 1 0600 270 7
0700 VRBL ltl 0700 270 7
0800 300 3 0800 270 7
0900 285 7
1000 285 8
1100 300 9
1200 300 9
1300 300 10
1400 300 10
1500 285 10
1600 285 9
1700 360 4 1700 270 9
1800 360 4 1800 270 9
1900 300 3 1900 8285
2000 VRBL 1 2000 270 8
2100 300 2 2100 270 8
2200 300 4 2200 285 4
2300 285 4 2300 270 3
2400 300 2 2400 270 7
APPENDIX I (continued)
DATE 10483 10583 10683
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 VRBL 1 0100 255 7
0200 225 2 0200 240 8
0300 150 2 0300 240 5
0400 195 2 0400 255 5
0500 255 1 0500 255 6
0600 240 2 0600 210 2
0700 210 1 0700 255 5
0800 240 3 0800 270 7
0900 300 4 0900 240 5
1000 300 5 1000 315 5
1100 270 9 1100 315 4
1200 270 9 1200 315 3
1300 240 10 1300 345 4
1400 240 8 1400 360 3
1500 240 7 1500 360 4
1600 225 8 1600 345 3
1700 285 5 1700 225 9
1800 270 2 1800 240 5
1900 270 5 1900 225 8
2000 270 6 2000 255 8
2100 270 3 2100 255 4
2200 VRBL 1 2200 270 7
2300 MISSING 2300 270 7
2400 MISSING 2400 255 7
APPENDIX I (continued)
DATE 1484 1584 1684
PST DRCTN SPEED PST DRCTN SPEED PST DRCTN SPEED
0100 060 6 0100 045 7
0200 060 7 0200 045 8
0300 060 5 0300 045 8
0400 060 6 0400 045 8
0500 045 6 0500 045 8
0600 045 6 0700 060 7
0700 045 middot 6 0800 045 6
0800 045 6
0900 045 5
1000 045 6
1100 060 6
1200 045 7
1300 045 6
1400 060 7
1500 030 6
1600 015 5
1700 015 4 1700 030 6
1800 015 4 1800 030 5
1900 015 4 1900 030 6
2000 030 4 2000 030 5
2100 030 5 2100 045 6
2200 030 5 2200 045 7
2300 030 6 2300 045 5
2400 030 6 2400 045 6
APPENDIX II SAN FRANCISCO BAY AREA
WEATHER FACTORS DURING SIX SAMPLING EPISODES 1982-84
BAY AREA WEATHER FACTORS Include
Mean wind speed in mph for Central (C) from SFO airport for North from BAAQMD Vallejo (VA) station for South from BAAQMD San Jose (SJ) station
Mean max temperature (deg F) for C averaged from SFO and SF for North from San Rafael (SR) for South from SJ
Total insolation in Langleysday as measured by Eppley pyranometer
Ventilation from OAK radiosonde data on 1 to 5 scale of increasing intensity with airflow direction at 1000 millibar level
Stability factor is temp (deg F) at 2500 feet minus that at the surface representing low-level inversion strength at Oakland OA Condord CC and SJ Vertical mixing decreases with algebraic value of stability factor
These data published monthly by the Bay Area Air Quality Management District Technical Services Division 117 in Contaminant and Weather Summary
APPENDIX II SAN FRANCISCO BAY AREA WEATHER FACTORS DURING 1982-1984 EPISODES
Date Mean wind Speed (mph) Max Temp (F) Insolation (LYday) Ventilation Stability Factor
C VA SJ C SR SJ SF SR SJ 4am 4pm OA cc SJ
August 1982 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 M 23 144 68 34 71 81 84 259 435 415 NW2 W2 25 20 17 T 24 12 2 67 3 1 63 79 77 185 438 380 W2 W2 9 9 3
Oct 1982 T 12 96 27 15 76 84 86 265 288 265 LVI 12 18 9 W 13 10 9 23 17 76 87 88 265 270 275 LVI
Th 14 151 23 1 7 62 74 75 202 222 215 WI NWI 12 15 9
May 1983 T 17 78 32 31 82 88 86 460 516 500 NI W2 15 13 6 W 18 12 1 29 34 76 87 90 433 492 485 SEI NWI 14 15 8
TH 19 66 30 34 88 92 90 469 528 490 LVI NES 10 8 2
September 1983 M 12 75 28 98 101 99 359 396 LVI NWI 17 22 12 T 13 150 43 78 91 89 369 444 WI W2 10 19 4 W 14 109 24 84 92 93 372 420 NWI NWI 20 21 13
Oct 1983 w 5 83 49 30 74 78 86 282 351 306 SI W3 10 15 15
TH 6 94 28 22 78 80 82 274 336 227 NW2 Wl 6 13 13
Jan 1984 w 4 79 81 1 0 58 54 62 141 144 125 EI NE2 8 11 9
TH 5 82 67 1 4 54 51 57 142 72 110 NEI SE2 14 15 10 F 6 80 76 1 0 54 49 56 160 81 85 EI NW2 19 20 14
APPENDIX III COMPLETE CORRELATION MATRICES FOR COMBINED EPISODES DAYTIME AND NIGHTTIME SAMPLES AND THE FOUR STATIONS
1 SAS 1 S 27 l~EDNESDA Y MARCH 13 1985
VARIABLE N MEAN STD DEV SUM MINIMUM MAXIMUM -middot- middot-middotmiddot bull-----middot--middot- bullr-bullbullmiddot-middotmiddot----middot- middot~bullmiddot--middot-bull------ --- ---middot-~---- ---middotmiddot middot------------middot
TA98P 72 1984166665 12 01082550 1428 5999988 0 60000000 58 39999998
TA9BM 72 9 14166666 5 67484565 658 1999995 o 40000000 26 79999995 -~--~bull~----- ---------- -~- --------
13AP 72 020000000 0 24321786 14 4000000 0 10000000 1 60000000
COR 72 0 58055556 0 39B81475 418000000 0 10000000 1 60000000
130 72 0 75000000 0 85B26553 540000000 o 10000000 5 10000000 1middot
PI3F 72 239 69152778 177 68068817 17257 7900000 17 00000000 950 00000000 I
13RF 72 44 50416667 34 50425341 3204 3000000 600000000 18400000000
KF 72 136 10416667 105 51221468 9799 5000000 31 00000000 491 00000000 -middot---- -- ----middot---middotmiddotmiddotmiddotmiddot middot- - --middot - middot-----middotmiddot---~- -- middot-middot ----middot
ZNF 72 24 71250000 1920486248 17793000000 300000000 123 00000000 I FEF 72 12533472222 101 30239095 9024 1000000 1200000000 45000000000
SIF 72 28335000000 242 67248939 20401 2000000 24 00000000 122000000000 middot- middot- ----middot-middotmiddotmiddot ~ --
CLF 72 288 53888889 527 75181308 207748000000 12 00000000 305000000000
NIF 72 7 79722222 883981027 561 4000000 200000000 4800000000
SF 72 1794 80000000 1319 22627505 1292256000000 442 00000000 7640 00000000 -- -----
N03 71 7 59577465 4 67578676 5392999998 3 00000000 24 50000000
co 54 1 09999985 0 46702578 59 3999917 0 19999999 2 79999924
NO 63 1 79047593 1 46702605 112 7999833 0 6 39999962 1 N02 69 2 59420248 1 27543350 178 9999712 o 09999996 629999924 I~
~ 03 69 l 99565192 1 45535861 137 6999827 0 5 89999962
802 69 0 36811586 0 75078232 25 3999946 0 4 29999924 I middotbull
1 I1 r-
CORRELATIONS OF COMBINED EPISODE DATA pp 1-5
18 15 27 l-JEDNESDAY MARCH L 1985 2
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O I NUMBER OF OBSERVATI l_S
TA98P TA9811 BAP COR BO PBF
-- ------ -middotmiddot
BRF ---- ---------
KF - - --- -middot --middot
ZNF FEF SIF
-middot--~---middot---- -----middot--
CLF NIF I a
I J1
TA98P 1 00000 0 0000
72
094186 0 0)01
72
0 45133 0 0001
72
0 54114 0 0001
72
060456 0 0001
72
0 27814 00180
72
039989 0 0005
72
0 26186 00263
middot 72
0 11718 03270
middot- 72
008699 0 4675
72
-001756 -026919 -009966 08836 00222 o 4049
72 72middot middot 72 --middot middotmiddotmiddot-
ibull 16
I middotbull
TA98M 0 94186 l 00000 0 48788 043885 0 59108 0 24562 037749 021840 0 12304 o 12537 001425 -022215 -007457 11
0 0001 0 0000 0 0001 0 0001 00001 00376 00011 00653 0 3032 02940 09054 00607 0 5336 1-i
72 72 72 72 72 72 72 72 72 72 72 72 72 1
BAP 0 45133 0 4878B 100000 03760B 092099 007810 0 30205 i)middot 15420 -0 -00763 -o 07278 -o 06918 0 01398-middot-0 t1687 middot - -- bull 7
0 0001 0 0001 0 0000 0 0011 o 0001 0 5144 00099 0 1959 09493 0 5435 0 5636 09072 03282 I B
72 72 72 72 72 72 72 72 72 72 72 72 72 19
(
COR 0 54114 0 0001
72
0 43885 0 0001
72
037608 0 0011
72
1 00000 00000
72middotmiddot
0 55756 0 70548 073679 0 5B534 0 26894 0 0001 00001 00001 00001 00224
72middotmiddotmiddot 72 72-middot ---middot middot middot middot 72middot-middotmiddotmiddotmiddot middot 72
028486 00153
72
0 13409 -o 14507 -020329 02615 02240 0 0868
72-- 12---middot-middot 72-middot- middot-
jI
i bullmiddot
BO 0 60456 0 59108 092099 0 55756 1 00000 0 19453 0431366 0 25566 008036 -005102 -008937 -0 05174 -o 11664 I~ Fgt
1n fl
Imiddotmiddotbull I
fBF
0 0001 72
0 27814 00180
72
0 0001 72
o 2462 00376
72
0 0001 72
o oeHt 0 5144
72
00001 00000 0 1015 00001 0 0302 middot 0 5022 middot 06704 0 4553 0 6660 03292 1-9
72 72 72 72 72 72 72 72 72 72 I o
2lmiddoto104e-middot--o-1c4~--1--ooooo---o--middotP0353--0middot831-i~~7---cr 7363emiddot-~-~20tmiddot-o- t47~----middotmiddotmiddot-middot t0 0001 o 1015 00000 00001 00001 00001 00001 00001 02149 0 1222 i72 72 72 72 72 72 72 72 72 72
If
middot BRF 0 39989
0 0005 72
0 37749 0 0011
72
030205 0 0)99
72
0 73679 0 0001
72-
043866 o 0001
72
0 90353 0 0001
72
1 0IJ000 0 82557 0 42057 00000 00001 0 0002
12-- -- 72--middot- 72
060402 0 0001
72
0 40616 -0 01936 0 14256 00004 08718 02322
72 middot - 72middotmiddot 72 -middotmiddotmiddot middot-- -
Hbull
1 middot-middot i
~bull
KF 0 26186 021840 0 15420 0 58534 025566 083143 082557 1 00000 0 43057 o 69375 0 56748 000848 020696 00263 00653 0 1959 00001 00302 00001 00001 00000 00002 00001 0 0001 09437 00811
72 72 72 72 72 72 72 72 72 72 72 72 72
ZNF 011718 0 3270
72
0 12304 -0 00763 0 3032 09493
72 72
0 26894 0 0224
72
middot 0 0B036 middot 0 5022
72
0 49237 0 0001
72
0middot42557-00002
72
0 4305-Y- middotmiddotL 00000 00002 000OIJ
72 72
0 51 986 0 0001
72
03036B 00095
72
middotO 07131--0 5516
72
030021 0 0104
72
middot-- ---f
- i
FEF 0 08699 0 12537 -007278 0 28486 -005102 0 73638 060402 069375 0 51986 1 00000 0 87518 -0 13744 044345 0 4675 0 2940 0 5435 00153 0 6704 00001 00001 0 0001 0 0001 00000 00001 0 2496 00001
I
72 72 72 72 middot 72 72 72--- --- middot 72--- 72 72 72 72 72 - - Jc fl
SIF -001756 001425 -006918 0 13409 -008937 0 52051 0 40616 0 56748 03036B 0 87518 1 00000 -o 10739 0 37160 0 8836 0 9054 0 5636 02615 0 4553 0 0001 00004 00001 00095 0 0001 00000 0 3692 00013
72 72 72 72 72 72 72 72 72 72 72 72 72 i 103
CLF -0 26919 -022215middot 001398 -o 14507 -005174 -o 14795 -001936- 0 00848 middot 0 07131 -o 13744middot -o 10139 1 00000middot -o 08486 middot - middot-middot - 114bull
0 0222 0 0607 09072 02240 06660 02149 08718 0 9437 0 5516 0 2496 03692 00000 0 4785 middotbull~
72 72 72 72 72 72 72 72 72 72 72 72 72
NIF -o 09966 0 4049
72
-o 07457 0 5336
72
-0 11687 0 3282
72
-o 20329 0 0868
72
-o 11664 03292
72
0 18383 0 1222
72
0 14256 02322
72
0 20696 0 0811
72
0 30021 0 0104
72
0 44345 0 0001
72
0 37160 -0 08486 0 0013 0 4785
72 72
1 00000 00000
72middot middot ---
11
-middot ~
middotc
3 SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROB) fRI UNDER H0RHO=O NUMBER OF OBSERVATIONS
TA98P TA98M BAP COR BO PBF BRF KF --- ~~~---- FEF ~---middot-CL----NIF 1 r
SF 0 21728 0 23319 0 27653 0 03011 0 36289 0 03302 0 24073 0 14947 0 14618 -0 07158 -0 03584 -o 03273 0 21207 li 0 0667 0 0487 0 0187 0 8017 0 0017 0 7830 0 0417 02101 02205 0 5502 0 7650 0 7849 0 0737 bull
12 12 12 12- 12 12 12 12 12 12 12 12 12 I middot --j
ND3 0 49496 0 51066 0 32107 0 14935 0 47658 -0 03134 0 16413 0 16149 0 22443 -0 08395 -0 07644 -0 01536 0 04641
00001 71
00001 71
00063 71
02138 71
00001 71
07953 71
01714 71
01785 71
00599 71
04864 71
05264 71
08989 71
07007 71
1t Ii
CQ 0 54527 0 0001
0 51478 0 0001
0 22569 0 1008
0 71090 0 0001
0 36294 o 0070
0 63471 0 0001
0 66256 0 49970 0 0001 middotmiddotmiddotmiddot 0 0001-
0 33739 - 0 0126
0 40650 0 0023
0 20033 0 1464
-0 05903 0 6716-
0 25321 0 0647 middot- -middot -
I
-1 54 54 54 54 54 54 54 54 54 54 54 54 54
gt ND 0 51037 0 44927 033604 049429 044249 0 48813 064595 0 37869 0 12802 027377 0 19516 -0 15416 0 14321 middot11
0 0001 0 0002 0 0071 00001 00003 00001 0 0001 0 0022 03174 0 0299 0 1253 0 2277 0 2628 bull
63 63 63 63 63 63 -middotmiddot 6-=-middotmiddotmiddot-middotmiddotmiddot --6~ -- - --- 63 63 63 __ --- -- _63- - - ~3 --- --- 11
ND2 0 32113 031262 0 10563 060602 0 17894 082420 069757 0 60710 043082 063826 047300 -0 12231 024964 i~ 0 0071
69 0 0089
69 0 3877
69 0 0001
69 0 1413
69 0 0001
69 0 0001
69 0 0001
69 -0 0002
69 0 0001
69 0 0001
69 0 3167
69 0 0386
69
- 1 t J
I 03 -0 27144 -0 35349 -0 40103 -O 1~963 -0 43105 -0 00401 -0 21271 0 04710 0 11161 0 18520 0 1901 -0 05802 0 07773 11
I 0 0241 -- - 0 0029- 0 0006 --02884 middot 0 0002 middot ~- 0 9739 middot middot middot 0 019a---0-700~---)--863middotmiddotmiddot 0 1276-----0 108(3-- --0middot0358--0-6i6S---------~ 69 69 69 69 69 69 69 69 69 69 69 69 69 10 f lS
802 0 04063 0 05412 -o 02478 -0 27496 -0 02399 -o 08152 0 06775 0 01647 0 04868 0 06690 0 12398 -0 03378- 0 33455 ---1 0 7403
69 0 6587
69 0 8398
69 0 0222
69 o 8449
69 0 5055
69 0 5802
69 0 8932
69 0 6912
69 0 5850
69 0 3101
69 0 7B29 0 0050 fi
69 69 I middotmiddot--- ---- middotmiddot-middotbullmiddot- -~----=middot=----~ -~- -~-~---- ~--1
SF N03 CO ND N02 03 S02
TA98P 0 21728 049496 0 54527 0 51037 032113 -027144 004063 0 0667
72 0 0001
71 0 0001
54 0 0001
63 0 0071
69 0 0241
69 0 7403
- 69-- -------- - - - - ---1
llltI--- - -- _lI
1middotmiddot 11i TA98M 0 23319 0 51066 0 51478 0 44927 0 31262 -o 35349 0 05412 I 1
00487 00001 00001 00002 00089 00029 ~6587 -~ 72 71 54 63 69 69 69 I
3AP 0 27653
o 0101 0 32107
o 0063 0 22569
o 1000 0 33604 -
o 0011 010563 -0 40103 -0 02478-
o a011 o 0006 o 0390 middot - - -- middotmiddot -~ - -- -middot --- - --rmiddot~I
1I 72 71 54 63 69 69 69 j
COR 0 03011 0 14935 0 71090 0 49429 0 60602 -0 12963 -0 27496 I- 1
0 8017 0 2138 0 0001 0 0001 0 0001 0 2884 0 0222 11middot 72 71 - 54 63 69 69 69 - - middot----- ~ --- bull middot ~ -
BO O 36289 0 47658 0 36294 0 44249 0 17894 -0 43105 -0 02399 bullf1~1
0 0017 0 0001 0 0070 0 0003 0 1413 0 0002 0 8449 middot~ 72 71 54 63 69 69 69 i
bull
P3F O 03302 0 7830
-0 03134 0 7953
0 63471 00001
0 48813 0 0001
082420 0 0001
-0 00401 0 9739
-009152 0 5055
- ~1bull
- 72 71 54 63 69 69 69 c I
bull bull
4 -AS 1527 WEDNESDAY MARCH 1i 19B5
CORRELATION COEFFICIENTS PROB ) IR I UNDER HO RHO=O NUMBER OF OBSERVATIOl~S -bull-----middot --middotmiddot middotmiddotmiddot---middot-- - middot--middot----- ----middotmiddot- -- - --- - -----
SF N03 co NO N02 03 S02
BRF 024073 o 16413 0 66256 06495 069757 -021271 006770 00417 0 1714 0 0001 0 0001 00001 00793 0 5902
72 71 54 63 69 69 69 ------middot-middotmiddot--middot------middot--- - -- ----middot middotmiddot- --middot- -- ~- --- -- --
bull
bull bullQ
KF 0 14947 0 16149 0 49970 037669 060710 0 04710 001647 Ij1102101 0 1785 00001 00022 00001 0 7007 08932 72 71 54 63 69 69 69
I ZNF 0 14618 o 22443 033739 o 12802 043082 0 11161 0 04868
0 6912 - -- ---- - --- -- -middotmiddotmiddotmiddot - - ---~-- ---middot---- ------~ ---- i II -02205 00599 0 0126 03174 00002 03613
72 71 54 63 69 69 69 ill
~middot ibull
FEF -o 011e -o 0039 040600 0 27377 063826 0 1020 o 0660 0 5502 04864 0 0023 00299 0 0001 0 1276 0 5850
72 71 54 63 69 69 69 ---~----- -- --- ---middot - --middot - ----- - ---middot- bull-------middot-middotmiddotmiddot---- -----~
zSIF -o 03584 -o 07644 020033 0 1916 047300 0 19001 0 12398 0 7650 0 5264 0 1464 0 1253 00001 0 1083 03101 1
middot- middot-middot - --- 72 71 4 63 69 69 69 3lt
CLF -0 03273 -o 01536 -005903 -0 15416 -0 12231 -005902 -003378 middot------ -middotmiddot --- --middot -middot middotmiddotmiddot-- ----~----- middotmiddotmiddotmiddot-- middot---~-----0 7849 o 898t middotmiddot o- onemiddot-- o ~2r--- middoto 3167middot---o 635B-- --o 7829middot---middot 3
lbull
3 72 71 54 63 69 69 69
I
NIF
SF
0 21207 0 0737
72
1 00000
0 04641 0 7007
71
0 46209
0 25321 0 0647
54
009243
0 14321 024964 0 07773 02628 00386 0 5255
63 69 69
0 12183 -002183 -026197
0 3345 0 0050
69
030023 - -- -middot---- -- --- ---middot --~- - middotmiddot--
13
1 i4 I 4
00000 0 0001 0 5062 03415 08587 0 0297 00122 72 71 54 63 69 69 69 i~
N03 0 46209 1 00000 022485 0 16421 -003172 -o 29535 038607 1 00001 0 0000 0 1055 o 2022 - -o 7973 00145 0 0011- --- ------- - - -- --- ---middotmiddot- - middotmiddot- - - ---- -- -- ---- ~
middot1-J
71 71 53 62 68 68 68 15middot
co 0 09243 0 22485 100000 0 67991 0 55757 -o 07620 0 12504
0 5062 54
o 1055 53
00000 54
00001 54
00001 54
0 5839 54
o 3676 54
51r ND 0 12183
03415 0 16421
02022 0 67991
o 0001 1 00000 00000
041523 00007
-o 27091 00317
037215 00027
5bull i
63 62 54 63 63 63 63 1111
jfJ
N02 -0 02183 o 8587
-0 03172 o 7973 middot
0 55757 00001
041523 0 0007
100000 00000
-o 08986 04628
-002262 08536 --- middot-- -- -middot-middot - ~--middot -
I61 timiddot
69 68 54 63 69 69 69 101 on
03 -o 26197 -029535 -0 07620 -o 27091 -008986 100000 -o 18398 0 0297 0 0145 0 5939 00317 04628 00000 0 1302
69 68 54 63 69 69 69 7
imiddot
SAS 1527 WEDNESDAY MARCH 13 1985
CORRELATION COEFFICIENTS PROBgt IRI UNDER HIJRHO=O I NUMBER OF OBSERVATIOl~S -----middot- -middot-middot----middot- -- --------~-----
SF N03 ca NO N02 03 802
802 0 30023 0 0122
69
0 38607 0 0011
68
0 12504 0 3676
54
0 37215 00027
63
-002262 08536
69
-o 18398 0 1302
69
t 00000 00000
69
I - --- - i1
I I middot(1
1middotmiddot 1
middot----middotmiddotmiddot-middot - -- -- -~---middot I_ in [111
(I
12 ~-- -- --- --------
I
M
IS
1(
I 11
1 1fi 1middotbullmiddot (bullfmiddot
I(
-1 bullbull~
middot n ~-I
l1
1middotbull
1 1f4
_-1~ f
~
_
fI
j 15 27 WEDNESDAY MARCH 1 1985 6 DN=D
VARIABLE N middotMEANmiddotmiddot middot -- ----sro DEV middot-------------SUM----- - --------middott1IltlMUt1middot---- MAXIUUM -(i
bull middot-- _4
TA98P 28 2202499999 1365803589 61669999959 440000000 5839999998
TA98M 28 9282142B5 6 20836076 middot259 8~82 --1 00000000 middot middot - ---middot ---middot26~--79999995 --~
BAP 28 0 16785714 0 09449112 4 70000000 o 10000000 0 40000000 1~ I
COR 28 0 70357143 041229452 1969999999 0 10000000 1 60000000 I
BO 28 0 74205714 0 57634132 -- -----middot--207~99--- middoto 10000000- ---- -middot--middot -2~0000000- middot
PBF 28 2562607143 14883820421 7174 33000000 49 oooooooo 63800000000
BRF 28 4605357143 2994573465 1289 50000000 8 00000000 114 00000000 I KF 28 14358214286 middot123 686401-70 4020--3000000()------ - --- - middot-- -36 00000000- ----bull-----91~--11
louZNF 28 31 75714286 22 74413931 88920000000 900000000 12300000000 -middot - - --
FEF 28 135 96428571 95 12233143 380700000000 28 bull 00000000 371 00000000 O SIF 28 - - -- 30b 18571429 middot --------- 268 5941502Bmiddot--middot-------B51k2ttt)OOOOO-------- ----- 24 00000000 --middot -------middot-t220-06600006--- j
31M
CLF 28 17468928571 261 58089088 489130000000 19 00000000 1450 00000000 13n
- 1_-
NIF 28 8 08928571 9 72973066 226 50000000 200000000 48 00000000 I )bullI
-SF 28 179 L 72500000 - 1285 52283891 - middot- - --501-68 -30006000 44200000000 middot-middotmiddot-7640-00000~-- -- - middotN03 27 798148148 3 53129275 21549999996 320000000 1580000000
co 21 1 21428562 0 39406297 2549999797 o 59999996 209999943
- l-~n I
NO 24 204166641 1 45659409 middot------- - 48 ~19392 - 0 50000000 - - 6-59999962-4
jbulll
IN02 27 2 58148094 105138633 6969998550 1 19999981 5 29999924 ilt
5103 27 2 88888863 1 38933659 7799999291 0 589999962
802 27 0 41851842 middot- middot -- 0 97179595 -------11 29919745 0 -+-29999924 --1~~ lll
I I I~
8~middot middot-- ~--~ CORRELATIONS OF DAYTIME EPISODE DATA pp 6-10 lU
I
-~-~----middot-i1
r
7 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
TA98P
TA98P
1 00000
CDRRELiTl ON COEFF IC I ENTS f PROB gt IR I
TA98M BAP COR BO PBF
094822 0 52984 0 50242 064686 0 19471
UNDER middotHOmiddotRHO-O--NUHBER---6F-8BSERVM 1-eNS
BRF KF WF FEF SIF
037528 0 24386 -0 14260 -0 11611 -0 11611
CLF
-o 19705
NIF
-o 32613
middotmiddot-middotmiddot ~---
g~
middot-
(I l - 1~bullbull
0 0000 0 0001 00037 00064 00002 0 3208 00491 0 2111 middot - O 4691 middotmiddotmiddot middot 0 5563 0 5563middotmiddot-middot 03149middot -- -0 0903
TA98M
28
0 94822 00001
28
1 00000 0 0000
28
0 57477 00014
28
0 37739 0 0477
28
0 59157 0 0009
28
0 06759 0 7326
213
029613 0 1260
28
0 09965 0 6139
28
-o 19311 0 3248
28
-o 18015 0 3590
28 28 28
-0 16029 -0 12647 -0 39751 0 4152 0 5213 00416
(I
I
[ 28 28 28 28 28 28 28 28 28 28 28 28 28 Ibullbull
~middot j- BAP 0 52984
0 0037 0 57477
0 0014 1 00000 00000
0 50692 0 0059
0 76753 0 0001
0 27670 0 1540
0 58768 0 0010
o 39484 00376
-o 18851 0 3367
0 04107 0 8356
o 14089 0 4745
-008588 06639
-o 19215 0 3273
~ I l
I
28 28 28 28 28 28 28 28 28 2B 28 28 28 middot~r 2
COR 0 50242 00064
037739 00477
0 50692 1 00000 00059- 00000
0 76463 o 0001
0 69824 00001
0 74394 0 0001 middot
0 66249 0 15168 0 18926 middot 0 0001--- 0~middot4410 middot-middot 0 3348-
0 15353 -001544 -0 32877 0 4354-- - 0 989--middot 0 0870-- ---
2
i 28 28 28 28 28 28 28 28 28 28 28 28 28
BO 0 64686 0 59157 0 76753 0 76463 1 00000 0 45571 07071 0 48410--0-00991 002665 0 04835middot-0051127--02460 2
00002 0 0009 0 0001 0 0001 00000 00148 0 0001 0 0090 0 9601 0 8929 08070 0 7800 0 2069 3
28 28 28 bull-- middot--middotmiddot-middotmiddot-- -bull--------- -
28 middotmiddotmiddot-- middot---
28 28 28 28 28 28 28 -middot -- ~- - --------------~----- ----~-------------- -~ -----bull-bull-~---middot ----middot--middotmiddotmiddot --
28 28 ~
bullbull- PBF o 19471 0 06759 027670 069824 045571 100000 o 86841 0 88081 036839 0 64672 0 53323 o 05644 -005948 middot 0 3208 0 7326 0 1540 0 0001 0 0148 0 0000 00001 00001 00537 0 0002 00022 0 7754 0 7637 3
28 28 28 28 28 28 28 28 28 28 28 28 28 - middot- 3
BRF 037528 0 0491
029613 0 1260
0 58768 0middot0010
0 74394 0 0001
0 71071 o 0001
0 86841 0 0001
1 00000 00000
0 86164 00001
0 18923 03348
0 48266 - 0 0093
0 42752 0 08228 middot 0 0232- --0 0772
-0 11217 --0middot 5o99----- -middot--
bull 28 28 28 213 28 28 28 28 28 28 2B 28 28
Ibull KF 024306 0 09965 0 39484 0 66249 048410 0 88081 086164 1 00000 middot 021847 0 664B6 0 57331 0041i163 004909 I~
0 2111 0 6139 0 0376 0 0001 0 0090 0 0001 00001 00000 o 2640 0 0001 00014 0 8295 08041 28 28 28 28 28 28 28 28 28 28 28 28 28
--- ---
ZNF -o 14260 -o 19311 -0 18851 0 15168 -000991 036839 0 18923 0 21847 1 00000 039592 o 11300 0 76033 0 22685 Ibullmiddot
0 4691 0 3248 0 3367 0 4410 09601 0 0537 03348 02640 00000 0 0370 0 5670 0 0001 02457 28 28 28 28 28 28 28 28 28 28 28 28 28
r I
FEF -0 11611 0 5563
28
-0 18015 0 3590
28
004107 0 18926 08356 0 3348
28 28
002665 08929
28
064672 00002
28
0 48266 00093
28
0 66486 0 0001-
28
0 39592 0 0370
28
1 00000 - - 0 0000
28
0 91240 0 19875 0 33503 o 0001 - o-a106- ----ooa14---middot
28 28 28
------middot----- r
51
sbull
SIF -o 11611 0 5563
-0 16029 0 4152
0 14089 0 4745
0 15353 0 4354
004835 08070
0 55523 0 0022
0 42752 00232
0 57331 0 0014
0 11300 0 5670
091240 0 0001
1 00000 0 0000
-o 10137 0 6078
0 24003 02186
I
1 28 28 28 28 28 28 28 28 28 28 28 28
28 -middotmiddot -~middot- --- j CLF -0 19705
0 3149 -0 12647
0 5213 -o 08588
06639 -001544
0 9379 -005527
0 7800 005644
0 7754 0 08228
0 6772 0 04263
08295 0 76033
0 0001 0 19875
0 3106 -o 10137
06078 1 00000
0 0000 0 15942
o 4110 1
I 28 28 28 28 28 28 28 28 28 28 28 28 28 fbull
NIF -o 32613 0 0903
-0 38751 0 0416
-0 19215 03273
-0 32877 0 0876
-024607 o 2069
-0 05948 0 7637
-0 11217 0 5699
0 04909 08041
022685 0 2457
0 33503 o 0814
0 24003 0186
0 15942 0 4178
1 00000 0 0000 - ~----
--- 7
28 28 28 28 28 28 28 28 28 28 28 28 28 7
_ ~d 1527 WEDNESDAY MARCH 1 1985 8 DN=D
(I-~-- CORRELATION COEFFICIENTS PROB gt IR I UNDlt -HO RHO=Omiddot -- NUMB~lt-oir-OltSEIWATlON9-- -- - ii 1 bull 3TA9BP TA98M BAP COR BO PDF BRF KF ZNF FEF SIF CLF NIF bull----- ---middot -- --- 1--
SF 0 22958 028128 0 53563 020299 044635 0 09855 0 32442 0 02425 0 00860 -0 14670 -0 0464 -0 03714 -0 02396 Ibull
0 2399 0 1471 00033 03002 0 0173 06178 0 0921 09025 09654 0 4563 08176 08512 09037 28 28 28 28 28 28 28 28 2e 20 20 - - - 2a-- -- middotmiddotmiddotmiddot middot 2s----- -middot - - I-
o
N03 0 55929 0 57045 0 65752 0 44922 064260 0 23458 049673 0 32987 0 22713 0 12396 006725 0 25440 -o 22887 1~ 0 0024 00019 0 0002 0 0187- 00003 0 2389 00084 00929 0 2546 0 5379 07399 0 2003 0 2508 -- I
27 27 27 27 27 27 27 27 27 27 27 27 27
I04
co 0 52641 041998 031521 065324 0 54453 061311 0 71 bUtmiddot- 0 51225 - 0 2670b 0 32003 0 21123 o~ oseoo-----0-41e--~- ----- -middot 1 0 0142 00580 0 1640 00013 00107 00005 00003 00067 02419 0 1573 03465 0 8028 0 0301 e
21 21 21 21 21 21 21 21 21 21 21 21 21 9
1-middot0 NO 0 49046 049033 046283 011591 044772 020150 o 52331 o 24250 -007607 000739 003584 -0 09097 o 15638
00150 00150 00228 0 5B96 00282 0 3451 0 0087 0 2536 0 7239 0 9727 0 8679 0 6725 0 4656 -_1
24 24--- 24- 24 24 24- middot middot 24--- -- middot- middot 24-- - 24---middot -- middot 24- - - 24-- -- middot-24-------24-----middot1 lfi
N02 023577 0 12295 0 18784 0 51300 025803 081394 060462 0 63894 0 49678 0 66543 0 56268 0 14308 -000258 27
bulla0 2364 0 5412 034B1 0 0062 0 1938 0 0001 middot 00008 00003 00084 00001 00023 - 0 4765- middot 0 9898 middot -- middot- -1
91
JO middotbull1 27 27 27 27 27 27 27 27 27 27 27 27 27 bull1 3
middot-1-o3- - middot-o- ~Toomiddot -omiddot35e37--omiddot-e3t02---0---03485- -o- 47e31- ---0-22480 -o-1-oltM2---o-1041~1gt~9----o--34eo---o-2trbullU-c---o--o4-431 ltr-02ttfl0---- 33 lmiddot1 0 1317 00681 00004 08630 00116 02596 0 5869 06050 02647 00774 0 1830 08263 0 8854 3~27 27 27 27 27 27 27 27 27 27 27 27 27
S02 -o 03006 0 00996 0 23266 -032781 000434 -o 10821 008671 -o 02683 -005085 002818 005407 0 01310 0 16543 0 8817 0 9607 0 2429 00951 0 9829 0 5911 06671 08943 08011 08890 0 7888 09483 04096
27 27 27 -- 27 27 27 - 27middot 27-- -middot middot 27---- 27 - 27 27-middot--- - -27 - - o
bull17
SF N03 co NO N02 03 S02 -1~
TA98P 0 22958 0 55929 0 52641 049046 023577 -029760 -0 03006 02399 00024 00142 - 00150 0 2364 0 1317 0 8817- --- - -- -middotmiddot - ------- middotmiddot-- - -- - ---
-l9 --- - - --- ---- E
28 27 21 24 27 27 27 middotbullo bullS
-~~TA98M 028128 0 57045 0 41998 049033 0 12295 -o 35637 000996
0 1471 0 0019 0 0580 00150 0 5412 00681 09607 ~gti 28 27 21 24 27 27 27 ~tmiddot
smiddot I lflBAP 0 53563 065752 031521 046283 0 18784 -063102 023266
0 0033 00002 0 1640 0 0228 0 3481 00004 02429 28 27 21 24 27 27 27
COR 020299 044922 065324 011591 0 51300 -003485 -o 32781 -------middot03002 00187 00013 0 5896 00062 08630 0 0951middotmiddot
28 27 21 24 27 27 27
BO 0 44635 0 64260 0 54453 0 44772 025803 -047831 0 00434 -- 4 0 0173 0 0003 0 0107 0 0282 0 1938 00116 0 9829 1
28 27 21 24 27 27 27 I
------middot-i=1 ~
middot1
9 SAS 15 27 WEDNESDAY MARCH 13 1985 DN=D
PSF
BRF
SF
0 09855 0 6178
28
0 32442 0 0921
28
CORRELAT IONmiddotmiddotCDEFFIC IENTB middotPROB gt middotIR I UNDER--middotHO RH0-0-r-NUHBER middotOF--OBSERlrlAT IONamp---- ----
ND3 co ND N02 03 902
0 23458 0 69311 0 20150 081394 0 22480 -o 10821 0 2389 00005 0 3451 0 0001 0 2596 0 5911
27 21 24 -- bullbull-middotmiddot- -~=-middotmiddot27 27 27
049673 0 71618 0 52331 060462 -0 10942 0 08671 0 0084 0 0003 0 0087 0 0008 0 5869 0 6671
27 21 24 27 27 27
----
-- --- middot---middotmiddotmiddotmiddot-bullmiddotmiddotmiddot -middot-
Ii 4 I
-- middotmiddot-middotmiddot )
1r
KF
ZNF
0 02425 0 9025
28
0 00860 0 9654
28
0 32987 0 0929
27
022713 0 2546
27
057225 00067
21
0 26706 02419
21
024250 0 2536
24
-o 07607 0 7239
24
063894 0 0003
27
049678 0 0084
27
0 10419 -002683 0 6050 08943
27 27
0 22249 -005085 02647 0 8011
27 27 --middotbullbull bull--bullmiddotbull---middot-middotmiddotmiddot---- --- - -- -- -- ----- ------ --
I1middotmiddot
I
- ----------- ----- -- -l FEF -0 14670
0 4563 28
0 12396 0 5379
27
0 32003 0 1573
21
0 00739 0 9727
24
066543 00001
27
0 34560 00774
27
002818 0 8890
27
SIF -0 04564 0 8176
28
006725 0 7389
27
0 -216-23 --0-031584middotmiddot 0 56ii16-B 03465 0 8679 0 0023
21 24 27
0-264Hr --0 05401------------- middotmiddotmiddot-middotmiddotmiddotmiddot------ ----0 1830 0 7888
27 27
--middotbullbull- ---------- - ----------- ------ -~------- ~4
CLF -003714 0 8512
28
025440 0 2003
27
005800 0 8028
21
-009097 0 6725
24
0 14308 0 4765
27
-004431 08263
27
0 01310 09483
27 middot ---- -----middotmiddotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddot -- - --middot -middotmiddot
NIF -002396 0 9037
28
-022887 0 2508
27
0 47369 0 0301
21
0 15638 0 4656
24
-000258 0 9898
27
002910 08854
27
0 1Ml43 0 4096
27
SF 1 00000 0 0000
28
020932 0 2947
27
0 24609 0 2822
21
026476 0 2112
24
-000797 -046722 0 9685 0 0140
27 27
009ii180 06452
27
middot---- middot- -- middot-- -- - --middotbull - - --j I
ND3 0 20932 0 2947
27
1 00000 0 0000
27
045740 0 0426
20
0 54089 0 0077
23
025211 0 2141
26
-041312 0 0359
26
0 31640 0 1153
26
[
------l co
NO
024609 0 2822
21
0 26478 02112
24
045740 0 0426
20
0 54089 00077
23
middot
100000 0 0000
21
0 82841 0 0001
21
082841 0 0001
21
1 00000 00000
24
0 54243 0 0111
21
0 13972 0 5149
24
001563 09464
21
-o 33512 0 1094
24
0 31080 0 1703
21
067986 0 0003
24
-middotmiddot -middot middot- - middotmiddot- --middot
Imiddot I
I
N02 -0 00797 0 9685
27
025211 0 2141
26
0 54243 0 0111
21
0 13972 0 5149
24
1 00000 0 0000
27
0 23446 0 2391
27
-0 01640 09353
27
oAS 1527 WEDNESDAY MARCH 13 1985 10 DN=D)
CORRELATION -COEFFICIENT PROB gt 1Rl middot UNDERmiddotHO-RHObullO---NVMBEt--W-OSSERVATIONS---------middotI
middotI) SF N03 co NO N02 03 902
i
03 -o 46722 -0 41312 001563 -033512 023446 1 00000 -o 41739) 00140 0 0359 09464 0 1094 02391 0 0000 003031middot
-middotmiddotmiddot -middotmiddot-middot-middot-middot -- --middot middotmiddot- -middotmiddot middot- - middot-- -----middot middotmiddot--middotmiddot--27 26 21 24 27 27 27j 802 0 09280 0 31640 o 31080 o 67986 -001640 -o 41739 1 00000
0 6452 0 1153 0 1703 00003 09353 00303 00000 27 26 21 24 27 27 27
~
middotmiddotmiddot------- 12
l)
I
1t
----- ----~----- --~middotmiddot -middot middot- middot---------------~-~-- --~--- ----middotmiddotmiddot
2
2
3
3
3-----------------j3 3
3
~
middot)
iibull i
bull middot middot middot
j5_bull obull f1 6
8 1J o
OF i6J -6f
f~
bull 1n
71
n - ------ ---middot--- --T- 1~
bull 74 7_
-
l
SAS 15 27 t~EDNESDAY MARCH 13 1985 11 DN=N
~-- ---middotVARIABLE N MEAN STD DEV --- -----middot-middotmiddotmiddot SUM---middot-- -- --middot--middot --- middot ---HI NI HVM - HAIEIHlJH
bullbull TA98P 44 18 45227271 10 76969236 811 89999920 060000000 43 19999993
TA98t1 44 905227272 5 38060636 398r9999963 -0 40000000 middotmiddot- --- middot-- ---- 23- 29999995 ---middot--
IMP 44 022045455 030160774 969999999 o 10000000 1 60000000
COR 44 0 50227273 0 37384777 2209999999 0 10000000 160000000
BO 44 0 75454545 1 00381934 33 19999998 o 10000000 5 10000000 --- ----- ~- --
PBF 44 229 16954545 19474778745 10083 46000000 17 00000000 950 00000000
BRF 44 43 51818182 3741857065 191480000000 6 00000000 184 00000000
KF 44 131 84545455 93 36273211 - - - - 5179 20000000 -- -- - --- 31 -00000000- - - - -~---- -483-- 00000000----
ZNF 44 2022954545 1520854380 890 10000000 3 00000000 74 00000000 middotmiddotmiddotmiddotmiddot-middotmiddot--- -
FEF 44 118 57045455 105 55881548 521 7 10000000 1200000000 450 00000000
- SIF 44 - 268 8181818i2 middot- middotmiddotmiddot 226 67652526 ----- -- -middot---11828middot00000000---middot- ----middot-------64cO0000000-- aeG--00000000-middot-
CLF 44 36098863636 63490915161 15883 50000000 1200000000 305000000000
NIF 44 7 61136364 8 33619778 33489999998 200000000 38 50000000
SF 44 1796 75681818 li35497035141 79057 80000000 442 00000000 middot--- middot- middot ---middot6780 00000800 --
N03 44 735909091 528205906 323 79999985 300000000 24 50000000
co 33 102727254 0 50017025 33 89999372 o 19999999 2 79999924
NO 39 1 63589716 1 47067583 6379998940 0-- -- -- ---- - 6 29999924 -
N02 42 2 60238061 1 41309002 109 29998565 009999996 6 29999924
03 42 1 42142833 1 19399613 5969998980 0 4 39999962
middot-middot-middot middot-middot middot-- - ---middot Q- -middotmiddotmiddotmiddotmiddot-middot--middotmiddotmiddotmiddotS02 42 0 33571422middot 0 67093710 1409999716middot 379999924- -middot I~
I
CORRELATIONS OF NIGHTTIME EPISODE DATA pp 11-15
1
~AS 15 27 WEDNESDAY MARCH bull 1985 12 DN=N
ti r-1
TA98P
CORRELATIOlit~OEFFlC IENT5
TA98M BAP COR
middotPROB
BO
I IH tJNoeft-1-1amp-RHObullomiddot-rNtlJ1BERmiddot1]F-oBSERVAilONS------- --~---~---~--
PDF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 0 0000
44
0 95237 00001
44
0 56104 00001
44
0 55072 00001
44
065764 00001
44
033045 00285
44
0 43091 00035
44
0 27040 0 34223 00759- middot- 00230
44 44
0 21529 0 1605
44
005318 -0 30865 0 10093 07317 - 0 04H----o- 5145-------
44 44 44
TA98M 0 95237 0 0001
44
1 00000 00000
44
0 55764 00001
44
0 50459 00005
44
063421 00001
44
0 35047 00197
44
0 43332 00033
44
0 33195 00277
44
0 46691 00014
44
0 32433 00317
44
0 1613B -0 27883 o 1se -02953 00668 02192
44 44 44 middot- middotmiddot---~- ---- - middotmiddotmiddot-middotmiddotmiddot---middot-
13AP 0 561Q4 00001
44
0 55764 00001
44
1 00000 0 0000
44
0 46158 00016
44
096100 0 0001
44
006291 0 6850
44
028304 00626
44
0 13823 03709
44
0 09523 -008884 -o 12002 0 5386 0 5663 04377
44 44 44
000207 09894
44
-o 11692 0 4498
44
COR 0 55072 0 0001
44
0 50459 046158 - 0 0005 --- O 0016
44 44 -
100000 0 0000
44
053818 00002
44
073445 00001
44
0 76993 0~0001
44
0 52936 0 27870 o 32813 009155 -o 14512 -o 12627 --- O 0002-----0 0670-- O Q2q7----o-5545-- 0 3473---o- 4141
44 44 44 44 44 44 - ---
Lshyi1middot
BO
PBF
0 65764 00001
44
0 33045 00285
44
063421 00001
44
0 35047 00197
44
096100 00001
44
006291 06850
44
0 5381B 0 0002
44
0 73445 00001
44
100000 0 0000
44
o 12564 0 4164
44
0 1264 0 4164
44 -middotmiddot middotmiddotmiddot- ~-
1 00000 00000
44
036631 00145
44
091786 00001
44
o 17730-o 2496
44
o 84828 00001
44 -
o 1~12 ~o 07102 o 3243 o6192
44 44
063036 o 77583 00001 0 0001
44 44
-o 15447 -o o~B1 -o 01oso-shyo3152 o 7284 o6479
44 44 44
0 51462 -o 18020 032380 0 0004 0 2410 00320
- 44 44 - 44
BRF 0 43091 00035
44
0 43332 0 0033
44
028304 0 76993 0 0626-- 0 0001 -
44 44
036631 00145
44
091786 00001
44
100000 -00000
44
0 84340 065557 -- o 0001- -o 0001-
44 j4
o 65958 o 0001
44
040304 -003362 029442 - e0061---0 0205---0 0524---
44 44 44
t1F 027040 0 0759
44
0 33195 00277
44
0 13B23 0 3709
44
0 52936 0 0002
44
0 17730 02496
44
0 84828 00001
44
084340 00001
44
1 00000 00000
44
0 70326 00001
44
o 73538 0 0001
44
0 55996 00001
44
001384 09289
44
035888 00167
44
ZNF 0 34223 00230
44
0 46691 00014
44
0 09123 0 5386
44
0 27870 00670
44
o 15212 03243
44
063036 00001
44
0 65557 00001
44
0 7036 00001
44
100000 00000
44
o 65550 00001
44
0 50242 -008205 00005 05965
44 44
--middot-middotmiddotmiddot- ---
0 39785 00075
44
I ji
FEF 0 21529 0 1605
44
0 32433 0 0317
44
-0 08884 032813 -007702 middotmiddot 0 5663 - middotmiddotmiddot O 0297 middot middotmiddot O 6192
44 44 44
0 77583 00001
44
065958 0 0001
44
0 73538 065550 100000 0 0001--- -0 0001-- -middotmiddotO 0000
44 44 44
086213 -020812 0 52012 -- 0-0001 middot--- -0 1752---0 0003-------
44 44 44
j
SIF 005318 0 7317
44
0 16138 0 2953
44
-o 12002 0 4377
44
009155 0 5545
44
-o 15497 03152
44
0 51462 0 0004
44
0 40304 00067
44
0 55CC6 0 0001
44
0 50242 00005
44
086213 0 0001
44
100000 -o 10747 00000 0 4874
44 44
0 18434middot 00009
44
n
CLF -0 30865 0 0415
44
-o 27883 0 0668
44
000207 -0 14512 -005387 09894 03473 0 7284
44 44 44
-o 18020 -003362 0 2418 08285
44 44
0 01384 -0 0B205 0 9289 0 5965
44 44
-020B12 -0 10747 0 1752 04874
44 44
100000 00000
44
-o 16495 02846
44
(
0
(
NIF 0 10093 0 5145
44
0 18899 02192
44
-o 11692 04498
44
-0 12627 -007080 04141 06479
44 44
032380 00320
44
0 29442 00524
44
0 35888 00167
44
039785 00075
44
0 52012 00003
44
0 48434 0 0009
44
-o 16495 0 2846
44
100000 - 0 0000 -
44
1 - ----
7
SAS 15 27 WEDNESDAY MARCH 13 1985 13 DN=N
CORRELATION COEFFICIENTS I PROB gt 1Rt UNDER-HO~RHObullO--t--NVHBE~-OF-OBSERVitiUONS--
I~TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF d
~SF 0 21660 0 20210 025827 -o 08092 0 34611 0 00377 0 20229 0 25261 o 29022 -003143 -o 02922 -o 03005 037826 70 1579 0 1883 0 0905 06016 00214 09806 0 1B79 0 0981 00560 0 B395 08507 0 8213 00114Imiddot
44 44 44 44 44 44 44 -middot 44 44 44 44 middot - - - 4+-middot-- -~middot middot- 44------middot- I(
IIND3 0 49232 0 50623 029892 000287 0 44009 -0 1203B 005446 0 07791 023518 -o 17030 -o 15959 -004835 0 17795 00007 00005 0 0487 09852 00028 0 4363 07255 0 6152 0 1244 0 2691 03008 0 7553 02478
44 44 44 44 44 44 44 44 44 44 44 44 44
co 0 54987 o 57589 027606 0 72226 033797 060931 065025 0 47550 036785 043089 o 11aoo -o 0+1aiii O uoae- --- ----middot --00009 00005 0 1199 00001 00544 00002 0 0001 0 0052 0 0352 0 0123 03357 0 7937 0 4021
33 33 33 33 33 33 33 33 33 33 33 33 33 c
2
iND 0 50903 0 41587 038206 0 70751 046865 061193 0 71055 0 49081 028361 039356 0 27777 -o 15733 o 15573 200009 00085 0 0164 00001 00026 00001 00001 0 0015 0 0802 0 0132 00869 0 3388 03438
39 39 39 -- -- 39 39 39 -- middot39 - 39 - 39 -- 39- ---- - 39 --- - 39 -- - ---39---~~-t
ND2 0 39623 0 42635 009859 0 70120 0 15866 0 83130 0 73349 0 62731 046326 063064 0 43895 -o 18107 0 39652 00094 00049 0 5345 00001 03156 00001 0 0001 0 0001 00020 -middot 0 0001 0 0036- - 0-2512- -0 0093 --
42 42 42 42 42 42 42 42 42 42 42 42 42
middot-03 -o 50293-0 47109 -o 41254- ---0-504 i e -0 52620 -0 19516middot -0 SMI 1 diams---0-0444-r-6-908-W-0--0082~---0-middot1-4amp4cmiddot--amp--06amp--amp--middotH-71 I 0 0007 0 0016 00066 00007 00003 0215 00210 07797 0 0471 0 5784 03649 0 7695 04588 middot 42 42 42 42 42 42 42 42 42 42 42 42 42
middot i S02 0 09780 0 09423 -o 08735 -o 27067 -00384 -o 07616 0 00639 0 05851 0 14078 0 09030 0 1775~ -o 04330 0 49077
0 5378 0 5528 0 5823 0 0830 0 8086 0 6317 0 7228 0 7128 03739 0 5693 02606 0 7854 0 0008 42 42 42 42 42 42 42 42 - 42 middot 42 - 42 -- -- 4i --middot - --42middot--------middot
SF ND3 co NO N02 03 802
TA98P 0 21660 049232 0 54987 0 50903 039623 -o 50293 009780 0 1579 0 0007 00009 00009 0 0094 0 0007 0 5378 ---middotmiddot--middot- middotmiddot-middot -- middotmiddotmiddot-middotmiddot middot- - -- - -- - -- -- - - -- ----- -middot - - I
44 44 33 39 42 42 42 i
TA98M 0 20210 0 50623 0 57589 041587 042635 -0 47109 009423 0 1883 0 0005 00005 0 0085 0 0049 0 0016 0 5528 ~44 44 33 39 42 42 42
- -middotmiddotmiddotmiddotmiddot-bullmiddotmiddot~ bullmiddot- middot- -middotmiddot middot--middot-- i I BAP 025827 029892 027606 038206 009859 -0 41254 -o 08735f1
0 0905 0 0487 0 1199 0 0164 0 5345 0 0066 0 5823 44 44 33 39 42 42 42 r
r COR -0 08092 000287 0 72226 0 70751 0 70120 -0 50418 -027067 s
_ - middot-middotmiddotmiddot-middot --middotmiddot j-_0 6016 09852 0 0001 00001 0 0001 0 0007 0 0830 44 44 33 39 42 42 42
BO 0 34611 0 44009 0 33797 0 46865 0 15866 -0 52620 -003854 1 0 0214 0 0028 0 0544 0 0026 0 3156 0 0003 08086
44 44 33 39 42 42 42 - --- middotbull 1
7bull
l 1527 WEDNESDAY MARCH 1 1985 14 DN=N
CORRELATION COEFFICIENTS PROB ) IR I UNDERmiddot-tlaquogt RHO=O -r--NUMBEftbullOF-oBIERVAT rems-----( a
SF N03 co NO N02 03 502 ]
bull bullI
PBF 0 00377 -0 12038 060931 061193 083130 -0 19516 -007616 bull 09806 04363 00002 00001 0 0001 02155 0 6317 bull44 44 33 39 42 42 42- middot 9
lo JgttBRF 0 20229 005446 065025 0 71055 0 73349 -035514 000639
0 1879 0 72 0 0001 0 0001 00001 00210 07228 iI 44 44 33 39 42 42 42 l
KF 0 2261 007791 0_470 0 49081 06273~ -004447 o oaoi-- -shy ---i- 00981 0 6152 00052 00015 o 0001 0 7797 o 7128 rnl
44 44 33 39 42 42 42 IJOI middot(bull
IZNF 0 29022 023518 036785 028361 046326 -o 30810 0 14078 imiddot 00560 0 1244 00352 0 0802 00020 00471 03739
39 middot ---- 42middot ----------44 44 33 42-- 42 middot--------~---middot----- ------------------ti 2s
FEF -0 03143 -o 17030 043089 039356 063064 00002 0 09030 v ~Ill
-- --~middotmiddotmiddot bull l - f08395 02691 00123 00132 00001 0 5784 0 5693 -I
44 44 33 39 42 42 42 31]
-1i
i - -- s1Fmiddotmiddot- -- --- -o02cn2 -o155J --0----11300--o--21111---o 43595---obull14342middot----o-t-T-5---------------- -------------------lt3~32
0 8507 0 3008 0 3357 0 0869 0 0036 0 3649 0 2606 31
1--44 44 33 39 42 42 42 i it(
CLF -0 03505 -004835 -004732 -o 15733 -0 18107 004660 -004330 -1bull108213 0 7553 0 7937 03388 02512 0 7695 0 7B54 44 44 33-- 39 42 42 42middot
~v
NIF 0 37826 0 17795 0 15085 0 15573 039652 0 11746 049577 0 0114 02478 0 4021 0343B 00093 0 4588 00008
middotbullll
lt1middot-
44 44 33 39 42 42 42 i
--- --- -middot-------- --SF 100000 0 57074 -000124 loz03909 -002841 -o 17580 0 4712~ 11H
bulll-1
00000 00001 09945 08132 08583 02654 00016 bullm
44 44 33 39 42 42 42 ii~ il
N03 0 57074 1 00000 0 12482 001750 -0 11774 -o 36096 0 4251 i10 0001 00000 0 4889 0 9158 0 4577 00189 00026 ~II
44 44 middot 33 39 42 42 42 - iL bullrn
co -000124 0 12482 1 00000 0 62874 0 57099 -o 36728 002018 09945 0 4889 00000 00001 0 0005 0 0355 0 9113
33 33 33 33 33 33 33 1
----- - ---- 08132 0 9158 00001 0 0000 00003 00042 0 4110
NO 0 03909 001750 062874 1 00000 0 54775 -0 44879 0 13543 Ofi
bullbull-J39 39 33 39 39 39 39 fill
fi
N02 -o 02841 -o 11774 0 57099 0 54775 100000 -028539 -002710 0 8583 0 4577 00005 0 0003 00000 0 0669 08647 7
n42 42 33 39 42 42 42
M
SAS 1527 WEDNESDAY MARCH 13 1985 15 DN=N
CORRELATION COEFF IC IENTB t middotPROB gt IR I UNDER- HO RHDbullO---NUMBER- OF-middotIBSERVATIOHS-----
SF N03 co NO N02 03 502
03 -o 17580 -o 36096 -o 36728 -0 44879 -o 28539 1 00000 -007679 0 2654 0 0189 0 0355 0 0042 o 0669 00000 0 6288
-~-middot -bull- -~middot --42 42 33 39 42 42 42 II
S02 0 47123 0 45251 0 02018 0 13543 -0 02710 -o 07679 1 00000 0 0016 0 0026 0 9113 04110 08647 06288 0 0000
42 42 33 39 42 42 42
i bull
bull
I i
middot
bullmiddot - --- bull
r
I I
iAS 1527 WEDNESDAY MARCH 18 1985 16 STATION=7430
VARIABLE N - -- MEAN middot STD DEV middot-middotbullmiddot------middotmiddotBUMmiddot--- -middot -middot -----middot------11ttlaquoMlfH- middot- Hifilll TMUM
I
middot
TA98P
TA98M
BAP
18
18
18
22 41111109
103499tttt
0 15000000
9 49122745
524182836
0 11504475
40339999966
1B6 ze 1 middot -
2 70000000
780000000 4100000000
3 40000000-------------middot-23-295- -
o 10000000 0 50000000
COR 18 0 52222222 039490215 939999999 0 10000000 160000000
BO 18 060000000- 0 5606553 10 80000000 middot middot o 10000000- --middot--- -----middotmiddot 2-00000000----bull
PBF
BRF
KF
18
18
18 middot -
25166666667
4283333333
1 57 -4444444 - middot
20844607146
41 58089210
-12b-202-561
453000000000
77100000000
78 00000000
1200000000
95000000000
18400000000 I~ tt-)()()0()00middot- 1
Imiddot -
ZNF
FEF
-sJFmiddot
18
18
18 - ---- ----
30 72222222
156 55555556
~33333333---------
14 74012354
11037381521
-21 t-555026t
55300000000
281800000000
middotmiddot----middot- 66()-00000000----- --- -
1700000000
2300000000
1 t 1 00000000
6700000000
-middot middot- - - - 1- 45000000000 3
3
l=1~ CLF
NIF
SF
N03
18
18
18
18
207 11111111
533333333
- 1450 -4444444 - -
8 30000000
327 61919948
330774492
638 56488658
5 45581179
372800000000
9600000000
2611 7middot00000000
149 39999992
1200000000
200000000
-- 442 uOOOOOOOmiddot--
3 50000000
- -
1400000000
----u9000000000
2409999996
3
3
3
4middot
4
4
4
co 18 0 94444434 0 58933865 1699999809 029999995 2 79999924
imiddot NO
N02
18
18
12888886
230555516
1 13131291
1 31930107
middot middot23-19999641 middotmiddot-
41 49999291
middot ----o-
0 09999996
--4- 00060()()(rmiddot
629999924
4
4
fit
0
1bull
II I
03
S02
18
18
2 32777747
0 12222221 -
167746482
0 17339364
4189999443
2-1999998 t - -
0 589999962
~I --o- - ------- ------o--5999999~-- t 51
51
o
o
CORRELATIONS OF PITTSBURGH EPISODE DATA PPo 16-19 SI a
7(
7
7 7
7
61
SAS 1527 WEDNESDAY MARCH 13 1985 17 STATION=7430
CORRELATION COEFFICIENTS PROB gt--1-R-t- VNOER-middot He-fUi0-0--middotN-bull middotte-----------
i TA98P TA98H BAP COR BO Pl3F BRF 11-F ZNF FEF SIF cu=middot NIF 1~ 4
1
TA98P 100000 091598 068417 063507 070777 0 45839 0 56313 0 48713 0 19524 035988 0 17180 -031142 072874 0 0000 0 0001 0 0017 0 0046 o 0010 0 0557 0 0150 0 0403 0 4875 middot 0 1424 -middot 0---4955---middot0 2084---0 0006-middot-middot-----
TA98M 0 91598 1 00000 0 74963 0 56550 0 71316 0 41446 0 54966 0 40132 0 30860 0 40986 0 18496 -O 15585 064087 00001 0 0000 0 0003 0 0145 0 0009 0 0873 00181 0 0988 02128 00912 0 4625 0 5369 00042 -
13AP 0 68417 0 74963 1 00000 082866 0 84923 0 63630 0 72735 0 49209 041453 0 40720 0 01378 -007288 0 49465 0 0017 0 0003 0 0000 middot 0 0001 0 0001 0 0045 0 0006 0 0360 0 0872 - 0 0935 0 9567 0 7738 middot middot 0 0369--middot--- -- -middotmiddot
COR 0 63507 0 56550 082866 100000 084966 082039 087254 0 75878 037503 049121 0 12672 -021349 O 57042 00046 0 0145 0 0001 00000 00001 00001 0 0001 0 0003 0 1252 0 0384 0 6163 - 0 3950 middot00134
BO 0 70777 0 71316 084923 084966 100000 0 54649 068519 0 55828 034814 0 17373 -021593 -005853 0 55791 0 0010 0 0009 0 0001----0 0001 0 0000 0 0189 - 0 0017 -- 00160~-01568--middot---04906 middot---0-3895--- 09176--00161----_------
PBF 0 45839 041446 063630 082039 054649 100000 097210 0 82598 047157 0 74449 033422 -022037 066759 o 0557 o 0013 o 0045 o 0001 o 0109 o 0000 o 0001 o 0001 o 0402 o 0004 o-11se o 3796 -- o 0025-- ----- --
BRF 0 56313 0 54966 072735 087254 068519 097218 100000 0 87204 046741 0 69153 027482 -O 14037 068301 o 0150-- 00101-- ooeeo--------0-0001 middotmiddot - o 0017 o 0001----o-oooo--o-0001---ooso5~--o0015-----middotmiddot0-697----amp--5-185------amp-oo1e f
3
KF 0 48713 040132 049209 075878 0 55828 0 82598 087204 1 00000 028700 0 63164 041478 -0 13133 0 59330 a
0 0403 0 0988 0 0380 0 0003 o 0160 0 0001 0 0001 0 0000 0 2482 0 0049 0 0870 0 6035 middot- 0 0094 --
ZNF 0 19524 030860 041453 037503 034814 047157 046741 0 28700 100000 026191 -004128 -o 12697 033862 l o 4375 o 2120 o 0012--- o 1252 o 1568 - o 0402 - o oso5 - o 248c----o 0000----- o 2939 -o-e7oe-- o-615o---o-1-69a--------------
bullI
FEF 035988 040986 040720 049121 0 17373 0 74449 0 69153 0 63164 026191 100000 082141 -0 35441 0 51473 0 1424 0 0912 00935 0 0384 0 4906 00004 00015 0 0049 02938 0 0000 00001 0 1490 00288 -
SIF 0 17180 0 18496 0 01378 0 12672 -0 21593 0 33422 0 27482 0 41478 -0 04128 0 82141 1 00000 -0 33167 0 19805 0 4955 0 4625 0 96o7 middot 0 6163 0 8895 0 1752 0 2697 0 0870- middot -0 8708 middot 0 0001 - 0 0000 - -- 0 178B-- ltgt-4-30B ------
CLF -031142 -O 15585 -007288 -021349 -005853 -022037 -0 14037 -0 13133 -0 12697 -035441 -033167 1 00000 -025158 0 2084 0 5369 0 7736 0 3950 0 8176 0 3796 0 5785 0 6035 0 6156 0 1490 0 1788 middot 0 0000 0 3139 -
NIF 0 72874 0 64087 049465 0 57042 0 55791 066759 068301 0 59330 033862 0 51473 0 19805 -025158 1 00000 00006 00042 00369- 00134 00161 0002s 00010 ----00094--0-1093middot 00200--- o-430B---oa1a9--ooooo---
middot SF 0 28894 0 31765 0 24930 0 18004 0 30830 0 16776 0 21522 0 16711 0 63384 -0 12749 -0 23080 -0 17360 0 21072 0 2449 0 1990 0 3185 0 4747 0 2132 0 5058 0 3911 0 5075 00047 06142 03568 0 4909 0 4013
N03 0 55567 0 0167
0 61048 0 0071
0 27834 0 2634
020313 0 4188
0 52764 0 0244
-0 12527 0 6204
0 03163 0 9008
0 03703 0 8840 middot
0 10979 middotO 6645
-0 26820 0 2819
-0 26761 0 2830
0 09971 033508 0 6938 ---middotO 1741-----~ middotf
co 0 70534 0 0011
0 70511 0 0011
0 72011 0 0008
0 77904 0 0001
065976 0 0029
0 77245 0 0002
0 81431 0 0001
0 68611 0 0017
0 69558 00013
0 59428 0 0093
0 27833 -021896 02634 0 3827
0 69202 00015
ND 0 58992 0 0100
0 50579 0 0322
0 55139 0 0177
0 56017 0 0156
042220 o 0809
0 68843 0 0016
0 70372 0 0011
0 67002 0 0028
037301 0 1274
062731 o 0053
034285 0 1637
-0 40289 0 0974
0 58109 0 0114--- -- - ~
--- ------ --
- d 1527 WEDNESDAY MARCH L 1985 18 STATION=7430
middotmiddotCORRELATION COEFFICIENTS 1 PROB --nu IJNOERHO~RHO=O r--N --is------middot-----------( l
TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NIF
N02 0 25001 0 22673 0 58716 0 74041 049444 083711 076285 0 45880 042236 0 53119 006999 -020935 0 50099 0 3170 03656 00104 00004 00370 00001 00002 00555 00808 00233 07826 04044 00342imiddotmiddot j
03 -033221 -049548 -038254 -0 12175 -045888 -000093 -0 13765 0 12685 -o 18999 023454 045794 -020550 -006538 0 1780 00365 0 1172 06303 00554 09971 0 5860 06160 0 4502 03489 00560 04133 0 7966
S02 -025143 -025953 -032437 -026536 -050654 -001752 -o 13897 -o 03603 0 10613 0 28547 048439 -021512 -020854 03142 0 2983 0 1891 02872 0 0319 0 9450 0 5823 08871 06751 02508 00416 03913 0 4063
-- middot~- ------ -----~-~F N03 co NO N02 03 802
TA98P 0 28894 0 55567 0 70534 0 58992 025001 -o 33221 -025143 0 2449 00167 0 0011 00100 03170 0 1780 03142
--middotmiddot-middotmiddot-middot ------- - -middot- ----------- ---~middot-middot---middotmiddot--middot---middot ------ - ----------
TA98M 031765 061048 0 70511 0 50579 022673 -049548 -025953 1 0 1990 0 0071 0 0011 00322 0 3656 00365 02983
-- middot- --- middotmiddot- --middotmiddot middot-- -middotmiddot-- middot-- -middot bull-middot middotmiddotmiddot-- -1 BAP 0 24930 0 27834 0 72011 0 55139 0 58716 -038254 -032437
03185 02634 00008 0 0177 0 0104 0 1172 0 1891 i - -- --------
COR 0 18004 020313 0 77904 0 56017 0 74041 -0 12175 -026536 0 4747 04188 00001 00156 o 0004 06303 02872
I 1-middotmiddot
I 130 0 30830 0 52764 0 65976 0 42220 049444 -o 45888 -o 50654 0 2132 0 0244 0 0029 0 0809 o 0370 00554 00319
------middotmiddot--------- --middot---- --- - middotmiddotmiddot-- - ----lmiddotmiddot
PBF 0 16776 -0 12527 0 77245 068843 083711 -000093 -001752 0 5058 06204 00002 00016 00001 09971 09450
13RF 021522 0 03163 081431 0 70372 0 76285 -o 13765 -0 13897 0 3911 0 9008 00001 00011 00002 0 5860 05823
--- -- ---------- ----middot- - ----- - -- --- middot- --~---- -- --- - - --- --- - ---
KF 0 16711 003703 068611 067002 045880 0 12685 -003603 0 5075 08840 00017 00023 00555 06160 0 8871
i ZNF 0 63384 0 10979 069558 037301 042236 -0 18999 0 10613I 00047 06645 00013 0 1274 o 0808 0 4502 06751
-middotmiddot-middotmiddotmiddotmiddot-middot
i FEF -0 12749 -026820 0 59428 062731 0 53119 023454 0 28547 06142 02819 0 0093 00053 00233 03489 02508 - - t
SIF -0 23080 -026761 0 27833 034285 006999 0 45794 0 48439 0 3568 0 2830 0 2634 0 1637 o 7826 00560 00416middot
---- ---middotmiddot --middot~--- middot-middot-middotmiddotmiddot- ---- middot-middotbull- middotmiddotmiddot-middot-middotmiddot--middotmiddotmiddot
CLF -0 17360 009971 -021896 -0 40289 -020935 -0 20550 -021512 le
0 4909 06938 0 3827 0 0974 o 4044 04133 03913
NIF 0 21072 0 33508 0 69202 0 58109 0 50099 -o 06538 -o 20854 170 4013 0 1741 00015 0 0114 00342 0 7966 0 4063
I
SAS 15 27 l~EDNESDAY MARCH 13 19B5 19 STATIDN=7430
CORRELATION CDEFFIC IENTS PROB
I
i SF N03 co NO N02 03
SF 1 00000 0 46453 0 37823 0 07208 006238 -031989 0 0000 0 0521 0 1217 0 7762 0 8058 0 19561middot
ND3 0 46453 1 00000 0 24259 -0 18670 -0 14874 -~ 45076 00521 0 0000 0 3321 0 4582 0 5558 0 0605
co 0 37823 0 24259 1 00000 0 71631 0 54136 -0 14710 0 1217 03321 00000 00008 00203 0 5602
NO 007208 -0 18670 0 71631 1 00000 034371 0 02900 0 7762 0 4582 00008 0 0000 0 1626 09091
ND2 0 06238 -0 14874 0 54136 0 34371 1 00000 -0 07769 0 8058 0 5558 00203 0 1626 0 0000 0 7593
middotmiddotmiddot------ middot--middot
03 -o 31989 -045076 -o 14710 002900 -007769 1 00000 o 1956 00605 o 5602 0 9091 o 7593 0 0000
gt-I RImiddot UNDERmiddotHe--RHO-o middot-fmiddot---N-----18--middot-- ---
802
001000 09686
-- middotmiddot~-middot--middot
-0 36811 0 1328
o 010s 0 9418
- - -- ~middot-----
0 04331 0 8645 middot
-o 12657 06167
middotmiddotmiddot- ---------middotmiddotmiddot--middotmiddot --------------middot ---middot-middotbull------~-----------------0 0537
o 0324 --- -middot -middot-- -------middotmiddot-
middot- 802 001000 -o 36811 001855 0 04331 -0 12657 0 50537 1 00000 0 9686 0 1328 0 9418 0 8645 06167 0 0324 0 00001bullI
t -------- - -------middot-- ---middotmiddot ---------- -middot---- -- middotmiddot-middot--bull------ ----~----middot-middotmiddotmiddotmiddot middotmiddotmiddot-middotmiddot--middot- ----middotmiddot ---~---- --iI
- 3 1527 WEDNESDAY MARCH 1 1985 20 STAT ION-=7433
VARIABLE
TA98P
N
18
middotmiddot MEAN
15 53333332
STD DEV
1160724924
-- - -- -middotSUM --- ---- middotmiddot
279 59999980
--~ middot-tummm middot
1 70000000
f1Aft
3800000000
2
3
4
0
7
TAJBM
BAP
16
18
0 2222222
0 18888889
470526100
0 17111705
124 -99P5
3 40000000
- middotmiddot--i 60000000middot
o 10000000
-middotmiddot middot----- 20-00000000----i~ 10
JI0 70000000 12
COR 18 060555556 038267206 1089999999 o 10000000 1 60000000
BO 18 0 70 080163232 13 OnflPtt middot - - --- o 10000000 - -- ----- --- 2-0000000 -
PBF 18 191 83333333 142 44844269 345300000000 4900000000 57600000000
BRF 18 38 72222222 26 73135536 69700000000 7 00000000 8400000000 KF 18 middotmiddotmiddot110tti-11111- 77 07947643 middotmiddot--- middotmiddotmiddot -middot--middot20PO 00000000 middotmiddot 31 middot-oooooooo-- ---~3a49-00000000--middot--j~
u
ZNF 18 23 16666667 2935432627 41700000000 3 00000000 123 00000000 I 2E
FEF 18 77 33333333 76 15309657 139200000000 1200000000 29000000000 12
SIF 1e-- --- -13a tJtt1-i 111------- - - middot --133-89334b0t- middot middot -- -----24-rr00000000----middot- ------ -24 -00()()()600- - 54---flfl-middotmiddot
3~ ~l~ 3gt
CLF 18 55633333333 921 65918162 1001400000000 1200000000 NIF 18 633333333 5 58358940 114 00000000 2 00000000 2000000000
SF 18 - 2409 il7777778 middot 196008414602 middot 433b7 00006000 -- 7B1 00000000 ---------middot---middot7b4ltrOOOOOOOO --
N03 17 720588235 409946194 122 49999993 350000000 1629999995
co 18 1 15555547 036817857 20 79999846 o 50000000 209999943
NO 18 -- 134999975 middot 120257059 - -- ---- - 24-~54s------ - -- - - --o -- middot- --------middotmiddot3-50000000 - f(
N02 18 2 21111060 1 12453320 39 79999083 069999999 5 29999924 gt
middot 03 18 222222193 129685385 3999999470 009999996 439999962 i 802 18 O 12222221middot 0 18959B81 - 2 - 1-1987 -- -- middot-- middot- middot middotmiddotmiddot-----0-middot - middotmiddotmiddot---middotmiddotmiddot-middot--middotmiddotmiddot- 0- sooooooo---r or
((
01
6
i middot-- -middot~-middot~- middotmiddot---middotmiddot- -middot~middot-middot--middot-middot
6 omiddot 6(
CORRELATIONS OF RICHMOND EPISODE OATA pp 20-24 6
6 7(
7
7 middot-----7
7 7(
SAS 15 27 WEDNESDAY MARCH 13 1985 21 STATION=7433
CORRELATION COEFF IC IENTB PROB gt 1R 1 UNDER HO RHO=O-- NUMBER OFmiddot -OBSERVATIEINS----middot----- 7-~ TA98P TA9BM BAP COR BO PDF BRF KF ZNF FEF StF CLF NIF
TA98P 1 00000 0 92786 069499 0 74542 0 87202 0 57443 0 80267 0 51850 0 30529 0 38214 0 52537 -028647 029335 00000 0 0001 o 0014 00004 00001 00127 00001 0 0275 02180 o 1176 00252 0 2491 middot bull-0 2374 --
18 18 18 18 18 18 18 18 18 18 18 18 18
TA98M 0 92786 l 00000 0 72027 0 55831 0 82658 0 36347 0 72067 0 30814 0 19909 0 183B1 0 27021 -o 24485 0 16441 00001 0 0000 0 0007 0 0160 00001 0 1382 0 0007 02135 0 4284 o 4653 02782 03275 0 5145
18 18 18 18 18 18 18 18 18 18 18 18 18 middot~ _ ~
IMP 0 694~9 0 72027 100000 026151 0 90959 0 02019 0 41595 0 08606 -003357 -0 09269 o 06630 -o 11526 -o 03899 0 0014 00007 0 0000 0 2945 o 0001 09366 00860 0 7342 08948 0 7145 0 7938 06488 0 0779
18 18 18 10 18 18 18 18 18 18 18 18 18
COR 0 74542 0 55831 026151 l 00000 0 55119 080568 0 79948 0 64018 0 55552 0 63819 0 71161 -0 17908 020556 0 0004 00160 0 29-45 -- 0 0000 0 0177 00001 00001 0 0042-- 00167 0 0044 - 0-0009-middot 0-4771 ---0 4132----~
18 18 18 18 18 18 18 18 18 18 18 18 18
BO 087202 082658 0 90959 0 55119 1 00000 030154 0 63241 0 29046 0 14882 0 16657 0 29835 -o 22686 middot 0 12310 --i 0 0001 0 0001 0 0001 0 0177 0 0000 0 240 00049 02423 0 5556 0 5089 02292 03653 0 6265
middot1 18 18 18 18 18 18 18 18 18 18 18 18 18rmiddot --- - middot-middotmiddot---bull middot-----middot __ _____ -middot-middot ~---- _ ____ -middotmiddot middotmiddotmiddot- -~---- -~-----------~-- ----~ --~-----------middot---------~--l-f1middot PBF 0 57443 0 36347 002019 0 80568 030154 100000 0 81421 0 87240 0 70828 083543 0 79259 -o 10927 0 58337
0 0127 0 1382 0 9366 0 0001 o 2240 0 0000 00001 0 0001 00010 0 0001 00001 0 6660 0 0110 18 18 18 18 18 18 18 18 18 18 18 18 18 -
BRF 0 80267 0 72067 0 41595 0 79948 063241 081421 1 00000 0 72937 0 59161 060433 o 58652 o 07669 0 34274 00001 0 0007 0-0860middot 0 0001 00049 00001 00000 00006 0 0097middotmiddot 0 0079 0 0105 bullmiddot- 0- 7628 ----0middot1638------
18 18 18 18 18 18 18 18 18 18 18 18 18
KF 0 51850 0 30814 008606 064018 029046 0 87240 0 72937 1 00000 0 70005 087520 0 85297 0 12863 0 58343 0 0275 0 2135 0 7342 0 0042 0 2423 00001 0 0006 00000 00012 0 0001 00001 0 6110 0 0110
18 18 18 18 18 18 18 18 18 18 18 18 18 -middot- middot-----~-- --
ZNF 030529 0 19909 -003357 0 55552 0 14882 0 70828 0 59161 0 70005 1 00000 087145 0 54483 0 11953 0 54444 0 2180 0 4284 08948 0 0167 0 5556 00010 00097 00012 00000 0 0001 00194 0 6366 0 0195
18 18 18 18 18 18 18 18 18 18 18 18 18
FEF 0 38214 0 18381 -0 09269 063819 0 16657 083543 0 60433 0 87520 0 87145 100000 0 78481 -0 00453 0 61174 0 1176 0 4653 0 7145- 0 0044 0 5089 00001 00079 0 0001-- --0 0001 -0 0000 -- 0-0001 -- 0 9858----- 0 00-10----- ----1
18 18 18 18 18 18 18 18 18 18 18 18 18i1middotmiddot
SIF 0 52537 027021 0 06630 0 71161 029835 0 79259 0 58652 0 85297 0 5~483 0 78481 1 00000 -007886 0 51571 0 0252 0 2782 0 7938 0 0009 0 2292 00001 0 0105 00001 00194 0 0001 0 0000 0 7558 00285
18 18 18 18 18 18 18 18 18 18 18 18 18 j ----bull--- - -middotmiddotmiddot -- middot-middot
CLF -0 28647 -o 24485 -o 11526 -0 17908 -022686 -o 10927 0 07669 0 12863 0 11953 -000453 -o 07886 1 00000 -0 20751 0 2491 03275 0 6488 0 4771 0 3653 06660 0 7623 06110 06366 0 9858 0 7558 0 0000 04087
18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 29335 0 16441 -003899 0 20556 0 12310 0 58337 034274 0 58343 0 54444 0 61174 0 51571 -o 20751 1 00000 02374 0 5145 0 8779 0 4132 06265 0 0110 0 1638 0 0110 0 0195 o 0070 0 0285 04087 0 0000 -- --- -- ---
18 18 18 18 18 18 18 18 18 18 18 18 18
-MS 1527 WEDNESDAY MARCH 1s 1985 22 STATION=7433
(i CORRELATION -COEFFICIENTS t middotmiddotPROB gt t R I UNDER-NO RH0-0-711UMBEftOF--osSERVATIONS
TA98P TA98M BAP COR BO PDF BRF KF INF FEF BIF CLF NIF
SF 0 71313 083969 0 71558 0 22603 o 72637 0 09862 0 44639 0 10128 -005963 -005255 0 12180 -030267 022105 00009 0 0001 00008 03671 0 0006 06970 00633 06892 0 8142 0 8359 06302 02222 03781
18 18 18 18 18 18 1B tamiddot middot 18 18 1B --middot - middot1e--middot-middot -18
ND3 0 70324 0 68520 0 57713 037124 069133 0 40748 0 55993 0 54401 0 50399 0 50803 0 47233 -o 14438 061873 00016 00024 00153 0 1423 0 0021 0 1045 00194 00240 00391 0 0373 00556 0 5B04 0 0081
17 17 17 17 17 17 17 17 17 17 17 17 17
co 066396 0 50083 022~12 08612 04336 0 76253 0 78881 O 723136 middot 0 60760 middot middot 0 67066 middot omiddot6H5P middoto 00752-0 l f23-middot---middot 0 0027 00343 03691 00001 00681 00002 00001 00007 00075 0 0023 0 0012 09764 06375
18 18 18 18 18 18 18 18 18 18 18 18 18
ND 0 83251 0 77972 067176 075225 0 77128 0 57718 087660 0 45750 0 37468 0 31146 037828 -003706 002979 200001 00001 00023 00003 00002 00121 00001 0 0563 0 1255 02083 0 1217 08839 09066 2 18 ----middotmiddot middot 18 - 1a-middot-middotmiddotmiddotmiddotmiddot 18 -middot-middot middot middot 18 bull- middot 10-- -- 1e-- ----1018 18 18 18 18 2 2
2N02 0 59259 039963 0 16270 067239 035817 089205 078246 0 92474 074285 087231 080553 005950 064767 -2
-middotmiddot- -- middot- 0 0096 0 1004 0 518yen 00022 o 1444 0 0001 00001 00001 00004 00001 00001 08140 00037 - 2
18 18 18 18 18 18 18 18 18 18 18 18 18 3
J1middot 03 - -o 3711o4middot -o 11~--o-e-04tfmiddot--o-middotoo44e- -o- 54332 -middot o te4ot -o 26Pttmiddotmiddot--o--241----o-30roPmiddot--03~---o-1l314t--o---oe3ampe---o-~1e 3 0 1213 00525 00024 09859 00198 0 4648 02796 03346 02151 o 1110 03555 08023 03107 318 18 18 18 18 18 18 18 18 18 18 18 18 3 -3
3502 0 75127 0 67523 073330 0 52519 0 78480 0 37019 0 57116 0 50172 044426 0 49609 0 55138 -o 08942 029820 30 0003 00021 00005 0 0252 00001 0 1305 00133 00339 0 0647 00363 00177 0 7242 02294
1B 18 18 18 18 1818 middot- middot- ie---middot- middot 18 te~- middotmiddot 18 middot- - middotmiddot1e----middotmiddotmiddot --1s--middot------- middot i
SF N03 co NO N02 03 902 I~
TA98P 0 71313 o 70324 066396 083251 059259 -037864 075127 middot - --- - ----- -- -- - --- -- ------- -f
bull1
00009 0 OOH middotmiddotmiddotmiddot 0 0027--- 0 0001 o 0096 0 1213 0 0003 middot middot ---- middot middot- 18 17 18 18 18 18 18
middotTA98M 083969 0 68520 0 50083 0 77972 039963 -o 46393 067523
Cl 00001 00024 00343 00001 o 1004 00525 00021
~~I 18 17 18 18 18 18 18 -middotmiddotmiddot-----middot ---- -- middotbull--- - middot- -middot-- middotmiddotmiddotmiddotmiddotmiddot--middotmiddot-middot-middotmiddot ----~--- - middot----- -- - - middot-middot ------ --middot--- --------- ----- -middot-middot-------middot-middotmiddot--middot ----- egt BAP 0 71558 0 57713 022512 067176 o 16270 -066946 073330
00008 0 0153 03691 00023 o 5189 00024 00005 (
1B 17 18 18 18 18 18 6bull
COR 0 22603 037124 0 86192 075225 067239 000448 0 52519 -- middotmiddot------
6~- 0 3671 0 1423 0 0001 - 00003 00022 0 9859 00252 ---- middot- middotmiddot-- ~----middot----------middot
i 18 17 18 18 18 18 18 o
130 0 72637 0 69133 0 43936 0 77128 035817 -o 54332 middoto 784Bo 00006 0 0021 00681 0 0002 o 1444 00198 0 0001
18 17 18 18 18 18 18 -------- lr
7
middot 7lt
17
- --- ---
SAS 1527 WEDNESDAY MARCH 13 1985 23 STATIONbull7433
CORRELATION COEFFICIENTS f PROB gt tRI -UNDER HORHO-O-f-NUHBER-eF-6fl8ERfATleNS----( I
SF N03
PBF 0 09862 0 40748 0 6970 0 1045
18 17
DRF 0 44639 0 55993 0 0633 0 0194
18 17
KF 0 10128 0 54401 0 6892 00240
18 17
ZNF -005963 0 50399 0 8142 0 0391
18 17
FEF -005205 0 50803 0 8359 0 0373
I 18 17 bull 1
1-middot middot - s IF - - middot middot middot o 121eo---o 47asa o 6302 0 0556 bullbullbull 1 18 17 middot
I CLF -0 30267 -o 14438bull1 1middot
02222 0 5804 18 17
NIF 0 22103 061873 0 3781 00081
18 17
i SF l 00000 0 64435 I 00000 00052
18 17 I
N03 0 64453 1 00000middotmiddotj 00052 00000 1middotmiddotmiddot 17- 17
111 co 0 15196 0 31686Imiddot
0 5472 02153 18 17
NO 0 48753 0 43096 o 0401 0 0842
18 17
ND2 0 14107 0 59138 b 5766 0 0124
18 17
2
co
0 76253
NO
0 57718
N02
089205
03
o 18401
802
0 37019 middot-- ---- middot--middot
3
bull-bullbull 0 0-gt02
18 0 0121
18 0 0001
18 0 4648
18 0 1305
18 middotmiddotmiddot---middotmiddotmiddot~- - -~--middot ~ ~ - -~- -~ -7
-middot - bull 10
0 78881 0 0001
18
0 72386
087660 0 0001
18
045750
0 78246 -026944 0 0001 0 2796
18 18
092474 024139
0 57116 00133
18
0 50172 -- -- --middotmiddotmiddot- --- --- -middotmiddot---
-If ---- -- -middot- --middotmiddot --r
00007 18
0 0563 18
0 0001 18
03346 18
00339 18
IA
060760 037468 074285 030709 o 44426 00075
-- 18 0 1255
---- 18 0 0004
18--0 2151
18 0 0647
10--middot-middot--- --middot-- middot middot------ ---- --middot-middot-middotmiddot middotmiddot --- -----middot ---- --------2
bullbull-------- - 2
21Of7066 031146 087231 038857 0 49609 00023 0 2083 00001 0 1110 00363 --middot-- middot-middot- - -- -- o
3018 18 18 18 18
-ltgt-bullbullbull- aeaa -- o aobullbullbull-middot -0 2314a omiddot ouaa ----- --~---middot-bull -middot~ - ~
0 0012 0 1217 0 0001 0 3555 0 0177 4 18 18 18 18 18 30
000752 -003706 0 05950 -006350 -o 08942 ltl0 9764 08839 08146 08023 0 7242 bull18---- 18-- 18 18 18 - - --- -middotmiddotmiddotmiddot- - ~---~-------~----- -bull-middotmiddot --- - - - ------- ~-- ---- ~ -~- -~
41
4
0 11923 0 02979 064767 0 25318 0 29820 06375 0 9066 00037 03107 0 2294
4018 18 18 18 18 4
015196 middot-0 -48753 0 14107 -0 44444 0middot57071 middot - -- --- -middot- middotmiddot- - -- middot--middot---middot - ~-middotmiddotmiddotmiddot-middotmiddot----- -----middot--middotmiddot----middot-middotmiddotmiddotmiddotmiddotmiddot-middotmiddotmiddotmiddot--middot -middot----~------
0 5472 00401 0 5766 00646 00134 18 18 18 18 18 -Imiddot
5bull1031686 0 43096 0 59138 -0 15354 0 78859 0 2153 00842 00124 0 5563 0 0002
middot - - - middot middot 1 7 __ -- 17middot middot middot 17 17 -1 7middot- -middot---middot- middot-middot -middotmiddot middot----middot --~------middot- middotmiddot-middotmiddotmiddotmiddotmiddotmiddot-middot-bull -----middot -middot-middotmiddotmiddotmiddot--middot-middotmiddot middot-middot middot--- middot---middotmiddot------ - SO
JUmiddot1 00000 0 74134 0 70880 -o 01013 0 51216 - -- -middot 1(~0 0000 00004 00010 0 9682 0 0298 -Oli
18 18 18 18 18 lo=bull 1r1
- -- middotmiddot- -~-- - =-middot---middotmiddotmiddotbullmiddotmiddot-074134 100000 0 55764 -0 53711 0 61918 - - - -middot -middot--middot--- 1~1 00004 0 0000 o 0162 00215 0 0061 lif
18 18 18 18 18 ltP
j1~1
bull1110 70880 0 55764 1 00000 0 05266 0 59471 I 0 0010 0 0162 0 0000 0 8356 00092 71i
18 18 18 18 18 --- -----~- -~- middot-middot middotl~1 ) Jr
_
SAS 1527 ~EDNESDAY MARCH 13 1985 24 STATION=7433
i i CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
SF N03 co NO N02 03 S02 l middot
03 -o 44444 -o 15354 -001013 -0 53711 005266 1 00000 -0 32031 bi 0 0646 0 5563 09682 00215 o 8356 00000 0 1950
18 17 18 18 18 18 18
b
802 0 57071 0 78859 o ~1216 061918 0 ~9471 -o 32031 1 00000 00134 00002- middot 00218 00061 00092 0 1950 00000
18 17 18 18 18 18 18
i 1111
1 ~
ilt1i -
i)
I middot
-- VARIABLEmiddotmiddot
TA98P
TA9811
BAP
CDR
N MEAN
18 27 34444442
18 12 22222221
18 o 32222222
18 0 87222222
SAS 1527 WEDNESDAY MARCH 13 1985 25 STATION=7440 f
STD DEV SUM HINH1UH 11A)( lMUM l l I------- -----1 13 76308883 492 19999905 7 70000000 58 39999999 I 1 -
I
6 1gt9245012 219 99999975 3 40000000 2b 79999995 1~1 -
0 42086124 5 79999999 o 10000000 160000000 11
036267885 1569999999 030000000 160000000 H BO
PBF
BRF
18 1 11gt111111
18 28700000000
18 52 00000000
130435420 20 89999999 o 10000000 5 10000000 1 111 14902348808 516600000000 8600000000 667 00000000 I J ~
I ~ middot1 I
1-middot11
3438B78066 93600000000 600000000 125 00000000
KF 18 13083333333
99 97249622 35500000000 3600000000 406-00000000 1middot1
ZNF
FEF
18 20 22222222
18 9322222222
middot bullbull 1
12 58643320 314 00000000 3 00000000 44 00000000 middot 11---- ----~--- --- --middot--------- middot- --bullmiddot--------middotmiddot- --~-------- -
40 25030659 1678 00000000 2000000000 18000000000 -
SIF
CLF
NIF
SF
16 20amp50000000
18 middot 126 00000000 -- ----- -~-~ middotmiddot-middot-middot--middot-middotmiddot -middot----middot- -- -- --~
18 266666667
18 middot middot 1350 55555556
--
bullbull j middot 99 44162878 3699 00000000 0100000000 446middot 00000000 middot I11i
i1
218 211H369 2277 00000000 1800000000 971 00000000 1
middot- - ------- - -middot---- -- -middot---------- -- ------ - ~------- 137198868 48 00000000 200000000 7 00000000
tbullmiddot 1111
95990466575 2431000000000 442 00000000 - middot - middot 4540 00000000 I ii
ND3 18 704444444 -- - -----
338391041 126 79999998 3 50000000 16 50000000 -- -- ---- - middotmiddot-middot middot- bull--middotmiddotmiddotmiddotmiddot---middot--- -
co 18 1 19999973 0 39704784 a 59999514 o 19999999 189999962
NO 18 227222183 1 600295-93 4089999300 009999996 b29999924 middot middot
ND2 18 3 17777745 i 028161550 07 19999409 1 89999962 500000000 -middot middot---~----- -middot- middot--
03 18 1 62222203 1 55433184 29 19999653 0 4 59999943
602 18 o 03888888 I bullbullI
008498365 019999987 0 0 29999995- I I
CORRELATIONS OF CONCORD EPISODE DATA pp 25-28
--
SAS 1527 L-JEDNESDAY MARCH 13 1985 26 STATION=7440
CORRELATION COEFFICIENTS PROBgt RI UNDER HORHO=O N = 18
- TA98P TA98M BAP COR BO PDF BRF KF ZNF FEF BIF CLF NIF
TA98P 1 00000 0 95880 0 33769 030796 045622 -o 14393 008990 0 05364 -o 13524 0 00460 -o 06952 002155 -001755 00000 0 0001 0 1705 0 2138 00570 0 5688 07228 08326 0 5926 09855 o 7840 09324 09449
TA98H 0 95880 1 00000 041939 0 16604 049250 -026445 -004611 -0 08562 -0 17367 -0 11225 -0 16946 0 01194 -o 13945 00001 0 0000 00932 0 5102 00379 02889 08558 07355 04907 06574 0 5014 09625 0 5810 middot
BAP 0 33769 0 41939 1 00000 0 18156 095321 -o 26383 0 15729 0 13137 -0 03319 -0 35950 -0 12397 0 54944 0 18677 0 1705 o 0832 00000 0 4709 00001 02901 0 5331 06033 08960 0 1429 06241 00182 04580
COR 0 30796 0 16604 0 18156 1 00000 035446 0 70265 0 79283 0 73934 -003594 060364 0 61514 -0 06136 077235 middot 1 02138 0 5102 04709 00000 0 1490 0 0011 00001 00005 08B74 00080 00066 0808 middot00002 - i
BO 0 45622 0 49250 095321 035446 100000 -0 14965 028353 0 20042 0 04606 -0 30491 -0 11295 0 51501 022571 - 1
00570 00379 0 0001 0 1490 0 0000 0 5534 02542 04252 08560middot 02186 06554 00287 0 3678 1 Ibull
i iPBF -0 14393 -0 26445 -o 26383 070265 -0 14965 100000 0 84410 0 73014 0 17409 084866 0 75510 -o 11898 063813
0 5688 - 0 2889 - 0 2901 -- 0 0011 0 5534 00000 middot00001 - 0- 0006 - O- 4896 - o 0001 - - o 0003 middot o 6382 - - 0-0044 - - I
I
BRF 0 08990 -0 04611 o 15729 0 79283 028353 0 84410 1 00000 085075 020290 065601 071360 030259 070691 i 0 7228 08558 o 5331 middot 00001 o 2542 00001 00000 0 0001 0 4194 00031 o 0009 o 2223 - o 0010 - H
JbullII
KF 005364 -o 08562 o 13137 0 73934 020042 0 73014 085075 1 00000 0 10793 0 70146 0 832all 0 22757 o 91863 I - ----middot- 0 8326 - o 7355- 0 6033 0 0005 04252 0 0006 - o 0001 0 0000- 06691 -00012 o 0001 - - o 3638 --o 0001 -~--------- -
111
ZNF -0 13524 -0 17367 -0 03319 -0 03594 004606 0 17409 020290 o 10793 1 00000 001902 o 06669 o 44606 -o 01121 i 0 596 04907 0 8960 middot 08874 08560 0 4896 o 4194 06699 00000 09403 0 7926 o 0635 0 7607 iJ
middot1 FEF 0 00460 -0 11225 -03~950 0 60364 -030491 084866 065601 0 70146 001902 100000 090712 -023023 060387
0 9855 o 6574 - 0 1429 - o0080 02186 00001 00031 0 0012 - 0 i403 o 0000 00001 03580 - 00080 I i SIF -006952 -o 16946 -o 12397 0 61514 -o 11295 0 75510 0 71360 083221 006669 0 90712 1 OObullJOO 003781 o 74978 j
0 7840 05014 06241 00066 06554 00003 00009 00001 0 7926 00001 00000 08816 00003 i i iI
CLF 002155 001194 o 54944 -006136 0 51501 -0 11898 0 30259 o 22757 044606 -023023 003781 100000 001395 09324 0 9625 -middot- 0 0182 -08089 00287 06382 - o 2223 03638 00635 03580 08816 00000 - o-1562 - I
lmiddotmiddotI 1bullbull 1middot
09449 0 5B10 0 4580 00002 0367B 00044 00010 00001middot 0 7607 00080 00003 09562 00000 NIF -0 01755 -o 13945 0 18677 0 77235 022571 063813 0 70691 0 91863 -0 07721 060387 0 74978 001395 1 00000
I SF
ND3
-0 00948 09702
0 57359 00128
-0 06773 0 7895
0 54898 00183
041263 00888-
0 70681 00010
001B84 09409-
037109 0 1295
045817 00559
0 62110 0 0001
004542 08580
-0 12277 0 6274
042099 00819
023617 03454
o 31931 0 1965-
0 19639 04348
0 61671 -0 15333 00064 0 5436
006757 -022576 0 7899 0 3677
005262 0 8357
-008816 0 7280
091598 00001
026757 02831
006616 0 7942
022764 03636
iCbull
i i
co 0 55631 0 0165
0 52842 00242
004224 08678
0 49836 00353
0 14993 0 5526
038285 0 1169
035844 0 1441
o 20851 0 4064
-o 20481 0 4149
030973 0 2110
0 18727 0 4568
-0 27334 0 2724
023756 03425
NO 0 32544 0 1876
0 25876 02998
021495 03917
0 75467 00003
035989 0 1424
0 62866 00052
0 69713 00013
0 50726 00317
-0 07765 0 7594
0 38188 0 1179
0 33233 -002472 0 1779 09224
0 51261 00296
SAS 15 27 l~EDNESDAY MARCH 13 1985 27 STATION=7440 I -
l
N02
TA98P
0 04264 0 8666
TA98M
004085 0 8721
CORRELATION
BAP COR
-o 26388 049516 02900 0 0367
COEFFICIENTS PROB) IRI UNDER HORHObullO I N bull 18
BO PBF BRF KF ZNF FEF
-024236 0 59937 036052 0 42562 -005869 0 64556 03325 00086 0 1416 00782 0 8171 00038
SIF
0 51792 00277
CLF
-0 37459 0 1256
NJF
045314 0 0590
--pmiddot1 _ ___ l-1 I I ~ i
i -
03 -o 08513 0 7370
-o 10636 0 6744
-o 40365 00967
-o 10841 06685
-039356 o 1061
0 16868 0 5034
-004380 o 8630
0 03076 0 9036
036536 0 1360
0 29733 02308
02893 -o 24712 02501 03228
000644 0 9798
))
S02 0 37814 0 40175 0 40203 -0 07740 031162 -o 11333 0 17914 0 13582 o 16193 0 00068 0 12285 0 68627 -o 08408 0 1218 0 0984 00982 0 7602 0 2081 06543 0 4769 0 5910 0 5209 09979 0 6272 00017 0 7401 middot
I
SF ND3 co NO ND2 03 SO I ) i
i I j
TA98P -o 00948 0 57359 0 55631 032544 004264 -008513 037814 11
0 9702 0 0128 o 0165 0 1876 o 8666 0 7370 0 1218 1-middotmiddot middotbull
TA98M -006773 0 54898 0 52842 025876 004085 -o 10636 04017 0 7895 0 0183 00242 0 2998 08721 06744 0 0984
- --middot -- middot- ------ - ---middot--middot -- --- - - -- ___ _ - __ -- __ __ _______ - -- -- - -- - --- --------- --middot 1
IMP 0 41263 0 70681 0 04224 0 21495 -026388 -o 40365 040203 1middotr 0 0888 0 0010 08678 0 3917 02900 00967 0 0982 I
-- -- -middot ---- ---~-- -middot- -middotmiddot I I
COR 0 01884 0 9409
0 37109 0 1295
0 49836 0 0353
0 75467 00003
049516 00367
-o 10841 06685
-o 07740 0 7602
- ----- ------- ----middot------ -----middot- middot--- --middot
-- --------middotbull--------- -1 ) BO 0 45817 0 82110 0 14993 0 35989 -0 24236 -o 39356 0 31162 i II
00559 00001 0 5526 0 1424 03325 0 1061 02081 I 11
I 4 I
PBF 0 04542 0 8580
-0 12277 06274
0 38285 0 1169
0 62866 00052
0 59937 o 0086
0 16868 0 5034
-o 11333 06543 i I
--- -- bull--middot ------middot i BRF 0 42099 0 23617 0 35844 0 69713 0 36052 -0 04380 o 17914 Ibullmiddot
KF
00819
0 31931
03454
0 19639
0 1441
020851
00013
0 50726
o 1416
042562
08630
0 03076
0 4769
0 13582
1ilvl
0 1965 0 4348 04064 00317 00782 09036 0 5910 bull I
--- --- -1middot ti
ZNF 0 61671 0 06757 -o 20481 -o 07765 -005869 o 36536 0 16193 )
00064 0 7899 0 4149 0 7594 08171 0 1360 0 5209 I
FEF -o 15333 -o 22576 0 30973 088188 064556 0 29733 000068 I 0 5436 0 3677 02110 0 1179 0 0038 02308 0 9979
i
6IF 0 05262 -008816 0 18727 033233 0 51792 0 28593 0 12285 1middot 11- I
08357 0 7280 0 4568 0 1779 o 0277 0 2501 06272 bull middot1
CLF 0 91 598 026757 -o 27334 -o 02472 -037459 -0 24712 068627 0 0001 0 2831 o 2724 0 9224 o 1256 03228 0 0017
NIF 0 06616 022764 0 23756 0 51261 045314 0 00644 -008408 0 7942 0 3636 03425 0 0296 0 0590 0 9798 0 7401
I -
--1
SAS 15 27 WEDNESDAY MARCH 13 1985 28 STATIONea7440
CORRELATION COEFFICIENTS PROBgt IRI UNDER HORHO=O N = 18 rmiddot SF N03 co NO N02 03 502
SF 1 00000 033200 -029567 -000496 -03B569 -0 14233 049893 1middot
ND3
co
NO
N02
03
502
0 0000
0 33200 0 1783
-0 29567 0 2336
-000496 0 9844
-0 3B569 0 1139
-o 14233 0 5732
0 49893 00351
0 1783
1 00000 00000
027495 02695
0 25388 03094
-0 34866 0 1562
001501 0 9529
0 12659 06167
0 2336
027495 0 2695
1 00000 00000
071100 00009
0 46975 00492
o 10103 0 6900
000000 1 0000
09844
0 2538B 03094
0 71100 0 0009
1 00000 00000
0 44577 00637
-o 15038 0 5514
001706 0 9464
0 1139 0 5732 00351
-034866 0 01501 0 12659 0 1562 0 9529 06167
0 46975 0 10103 000000 0 0492 06900 1 0000
044577 -0 15038 0 01706 00637 0 5514 09464
1 00000 000732 -o 11744 o 0000 0 9770 06426
000732 100000 -o 16279 09770 00000 0 5187
- -
-o 11744 -o 16279 100000 06426 0 5187 00000
-- --~-- ---------- - - ---middot
ibull middotmiddot jmiddot I jbull Imiddot i1bullj lllj
11middot I bull
1- bulli 1 I ik1 jJ~ -middotgt ~ llli
11 4
----- -~- ---------i ~
II-1lt1
41
-1middot_I j
_
) I
1bull bullI I
[
~-- J
-i I I
_
_
i _
i i
I I -_
SAS STATION=7996
15 27 WEDNESDAY MARCH 13 1985 29 l -
VARIABLE
TA98P
N
18
MEAN
1407777777
STD DEV
8 17554139
SUM
25339999978
MINIMUM
o 60000000
MAXIMUM
28 39999998
Imiddot1 I
middotmiddotmiddotmiddoti TA98M
BAP
CDR
18
18
18
707222222
0 13888889
032222222
426391225
006978023
025565500
12729999995
2 50000000
580000000
040000000
o 10000000
o 10000000
t4 20000000
0 30000000
090000000
I
middot1
BO
PBF
BRF
KF
ZNF
FEF
SIF
CLF ---bull middot--middot ---
18
18
18
18
18
18
18
18
o 48333333
22826611111
44 46111111
139 52777778
24 73888889
17422777778
450951555556
26421111111
031482955
20203637gt56
3533125826
115 77552218
15 52118624
125 44174090
33441987385
21783477519
B 70000000
4108 79000000
BOO 30000000
2511 50000000
44530000000 ~---middot- middot--
3136 10000000
middot 8117 20000000 middot
4755 80000000
--
o 10000000
1700000000
700000000
3700000000
400000000
1700000000
7900000000
1900000000
1 20000000 I 11
77100000000 middot1 1-li
13000000000 middot- 11
middot11middot43700000000 I
i-11 7400000000 middot-I
------middotmiddotmiddotmiddot-middotmiddot -- -1-middot~I421 00000000 bullI
ii - middot- middot-middot middotl 220 00000000 middotmiddotmiddot1~
Ibull
89300000000 i~I middot-------middot- - -------- -------- (
NIF 18 1685555555 1260598468 303 39999998 200000000 48 00000000 1
SF
N03
ND
18
18
9
1968 4222222
781111111 --middot-- middot-middot- ---
2 71111094
115393953280
565174506
1 72224005
35431 60000000 middot
140 59999998
24 39999843
54100000000
300000000
029999995
5790c 00000000
24 50000000
6 39999962
bulliI _t
I I
I
ND2 16 269999966 149092499 4049999332 l 19999981 b 19999981
03 15 1 77333314 1 20621393 26 59999704 middot-middot - -
0 3 19999981
S02 15 1 35333300 1 14633970 2029999506 029999995 4 29999924
middotmiddotmiddotmiddotmiddot1middot
i middotj
bull-li
CORRELATIONS OF MARTINEZ EPISODE DATA pp 29-33 middot1
--
SAS 1527 WEDNESDAY MARCH 13 1985 30 STATION=7996
CORRELATION COEFFirIENTS PROBgt IRI UNDER HORHO=O NUMBER OF OBSERVATIONS
TA9BP TA98M BAP COR BO PBF BRF KF ZNF FEF SIF CLF NIF
TA98P 1 00000 o 92935 0 28825 -o 01129 048961 0 13388 033461 0 18025 0 13720 -002539 -0 16409 -o 32350 0 10007 00000 00001 02461 09645 00392 05964 0 1747 0 4742 05872 09204 o 0153 0 1904 06928 i
18 18 18 18 18 18 18 18 18 18 18 18 18 1d
TA98M 092935 1 00000 032610 0 15817 046062 033824 0 47603 034902 033729 0 16881 0 01959 -026313 0 12028 rmiddot ii 00001 00000 0 1866 0 5308 00544 0 1698 00458 0 1557 0 1711 0 0031 09385 02914 06345
I18 18 18 18 18 18 18 18 18 18 18 18 18 i
1
I BAP 028825 032610 1 00000 070710 083451 0 57460 o 72955 0 55650 0 34666 0 43439 0 36029 -o 25018 -0 23398 bullmiddotmiddot i --
I02461 0 1866 00000 00010 00001 00126 00006 00165 0 1587 00717 0 1419 03167 03501 18 18 10- 18 18 18 18 18 18 18 18 18 18 - i
I(
COR -o 01129 0 15817 0 70710 1 00000 063339 0 84473 084957 0 79294 0 54174 0 76B34 072613 -001103 -0 19023 middotI09645 0 5308 00010 00000 00048 00001 00001 00001 00202 00002 00006 09653 0 4496 middotI18 18 18 18 18 18 18 18 18 18 18 18 18 bull
I BO 0 48t61 - 0 46062 --0 83451-- 0 6333t 1 00000 0 45616 --o 6738B middotmiddot 04635middot-0-23343 middot 0middot21588 middot 0-21759--0 23724 -03382B------middot-- Imiddotmiddot1
00392 00544 00001 0 0048 00000 00571 00022 00494 03512 02678 03858 03432 0 1697 JIbull
18 18 18 18 18 18 18 18 18 18 18 18 18 i~1 J-llPBF 0 13388 033824 057460 084473 045616 100000 092944 0 92958 074960 090022 0 74867 -o 05122 0 18641 I j~))0 5964 0 1698 00126 00001 o 0571 00000 00001 0 0001 0 0003 00001 00004 08400 0 4589 I1a--- -----middot -1a - - 10- 18 - --- ---is-- -- -1a ------10--- -- 18 - -1a------ -1s---- -------18 - 18 18 I i ~~BRF 0 33461 047603 0 72955 0 84957 067388 092944 100000 0 84864 068574 0 76972 0 59950 -o 12210 006953 I hi
0 1747 o 0458 - 0 0006 - 00001 00022 00001 00000 - 0 0001 00017 00002 00085 06294 0 7840 18 18 1B 18 18 18 18 18 18 18 18 18 18
KF 0 18025 0 34902 middot 0 55650 -- 0 79294 046f35 09258 084864 1 00000 - 0 65671 o 80442 -o 6983_1 -middot o 00024 o 097c3- - - - I 0 4742 o 1557 00165 00001 00494 00001 00001 00000 00031 0 0001 0 0013 0 9993 0 6991 1
18 18 18 18 18 18 18 18 18 18 18 18 18 ) 1)
ZNF 0 1370 03379 034666 0 54174 023343 074960 068574 065671 1 00000 0 72305 0 54970 -o 18941 049618 I li0 5872 o 1711 0 1587 00202 03512 00003 00017 00031 00000 00007 00181 04516 00362
---- -- 18 1e-- - middot 1a--- 18 18 18 18 -- - --18 - --- - 18 middot middot - - 1B 18 middot 18 middot---- -middot 18 - middot- I
~ i bull FEF -0 02539 0 16881 0 43439 0 76834 027588 090022 0 76972 0 80442 0 72305 1 00000 090809 -0 118f4 033937
I 0 9204 0 5031 00717 00002 02678 0 0001 00002 0 0001 00007 00000 00001 06406 0 1683 middotmiddotI
18 18 18 18 18 18 18 18 18 18 18 18 18
JSIF -- --o 16409 001959middotmiddot0 360~middot0 72613 021759 0 74867 0 59~50 - 0 69831-- 0 54970 010809 1 00000 0 15372 0 14030- I I 0 5153 09385 0 1419 00006 03858 00004 00085 00013 00181 00001 00000 05425 0 5787 middot
18 18 18 1B 18 18 18 18 18 18 18 18 18 1middotmiddotmiddot]--middot1 jugtj
CLF -0 32350 -0 26315 -0 25018 -001103 -023724 -005122 -0 12210 0 00024 -0 18941 -o 11814 0 15372 100000 -027728 1
0 1904 02914 03167 0 9653 03432 08400 06294 09993 0 4516 06406 0 5425 o 0000 02653 -18 18 18 18 18 18 18 18 18 18 18 18 18
NIF 0 10007 0 12028 -o 23398 -0 19023 -0 33828 0 18641 0 06953 0 09793 0 49618 0 33937 0 14030 -0 27728 100000 0 6928 06345 03501 0 4496 o 1697 04589 o 7840 06991 0 0362 o 1683 0 5787 02653 00000 1
18 18 18 18 18 18 18 18 18 18 18 18 18
SAS 1527 WEDNESDAY MARCH 13 1985 31 STATION=7996
CORRELATION COEFFICIENTS I PROB gt IRI UNDER---HQmiddotRH0-O--f-NUMBER--OFmiddot-OBSERVATIONS-middot 1~ TA98P TA98M BAP COR BO PBF BRF KF ZNF FEF BIF CLF NlF middot1
bull SF 0 51471 0 5-1491 0 04099 -002761 0 18682 o 15363 023184 0 33801 036622 0 01413 -001806 008135 0 23057 bull bull 10 0288 0 0288 08717 0 9134 0 4579 0 5428 0 3546 0 1701 0 1350 09556 09433 0 7483 0 3573middot 18 18 18 18 18 18 18 18 18 18 - 18 - --- --- ta----- --- -18middot ---middot--- bull c
N03 0 63242 0 56885 0 15694 -000873 0 46691 -0 10536 0 10681 0 06973 006362 -0 26846 -023405 0 06398 -023346 II
I-0 0049 0 0138 0 5340 0 9726 0 0508 0 6773 0 6731 0 7834 0 B020 02814 03499 08009 0 3512 18 18 18 18 18 18 18 18 18 18 18 18 18 i
11bull ii(
co ---- middotmiddotmiddot-middot-- ii li iI[0 0 0 0 0 0 0 0 0 0 0 0 0 1
NO 0 55212 0 48690 082799 051547 0 73964 036537 o 5~405 0 17045 0 43112 0 13157 -o 01367 -o 31045 -o 14897 1 0 1232 0 1838 0 0058 0 1555 0 0227 0 3336 0 1217 0 6611 0 2466 0 7358 0 9722 0 4162 0 7021
9 - 9 - 9 9 9 - 9 - 9-- -- - ---9--------middot --- 9------ - -- middot9------ --------9--- ------middot----9------- --- -middot 9-----~--tImiddot N02 0 29052 0 51279 0 41615 0 74490 033341 0 93532 0 83513 0 85814 074557 093257 089792 -0 16144 032692 i 0 2935 0 0506 0 1229 0 0014 0 2246 00001 00001 00001 00014 00001 0 0001- --- 0 5654- 0 2343 --- ---- - i
llt
I 3
l -----oa --0 4 705 l- ---0 -53725--0 -485-4amp---0--61 l 88 -0---62129 -O-i4779 -0 4amp19amp-middot --0 24aee--0---31080- -OcmiddotO1amp1-2--e middot04-ca9---0-d 5703 G---QSH 8 middotff
I 15 15 15 15 15 15 15 15 15 15 15 15 15
rj 00767 00389 00666 0 1729 00134 03732 00908 03811 02595 09573 08808 0 5762 03102 l
15 15 15 15 15 15 15 15 15 15 15 15 15 3i ~802 0 73863 0 58663 041270 -001688 0 52023 -o 14223 0 14874 -o 06508 -004904 -o 32131 -031231 0 15680 -022241 n0 0017 00215 0 1263 0 9524 00468 06131 0 5968 0 8177 08622 02429 02571 0 5768 04256
16 16 15- ---- - 15 15 15 15 15-- - 15 -- 15 -- --15 --15------ --- -15------ -- middot
middot I
SF N03 co NO N02 03 802 middottmiddot _ middotIlt
TA98P 0 51471 0 63242 0 55212 029052 -o 47051 0 73863 0 0288 00049 0 1232 02935 00767 0 0017 -~--er--~bullmiddot~
18 18 0 9 15 15 15 1 iIll
TA98H 0 51491 0 56885 0 48690 0 51279 -0 53725 0 58663 Imiddotbull0 0288 0 0138 0 1838 0 0506 0 0389 0021 i1bull
bulls_18 18 0 9 15 15 15i -- ----------[
BAP 0 04099 0 15694 082799 041615 -0 48545 0 41270 0 8717 0 5340 0 0058 o 1229 0 0666 0 1263 Imiddotimiddot 18 18 0 9 15 15 15 I_
t1
COR -o 02761 -0 00873 0 51547 074490 -0 37138 -001688 04
Imiddot 0 9134 0 9726 0 1555 00014 0 1729 09524 - middot-middotmiddotmiddot --middot-middot-~middot-middotmiddotmiddotmiddot--~- ~middot~--~-- I 18 18 0 9 15 15 15 I ~~
BO 0 18682 0 46691 0 73964 033341 -062129 0 52023 lti 0 4579 0 0508 0 0227 02246 00134 0046B 1(l
7118 18 0 9 15 15 15 --- - -middot ~
iS 1527 WEDNESDAY MARCH 19B5 32-STATIONbull7996
CORRELATION COEFFICIENTS PROB) IRl UNDER HORHObullomiddotrmiddotmiddotNUMBeRmiddotop---oeSERVATfONS--middot- -
3 2
SF N03 co NO N02 03 902 3
4
bull PBF 0 15363 -0 10536 036537 093532 -0 24779 -0 14223 bull
0 5428 0 6773 03336 0 0001 03732 06131 middot~- -middot middotbull--middotmiddotmiddotmiddot~ bull18 18 0 9 15 15 15
BRF 0 231B4 0 106B1 0 55405 083513 -045195 0 14874 I
0 3546 0 6731 0 1217 00001 00908 0 596B 18 18 0 9 15 15 15
Imiddot
KF 0 33801 0 0673 0 17045 085814 -024388 -006508 - -- - --- - - middot- 0 1701 0 7834 0 6611 o 0001 03B11 08177
18 18 0 9 15 15 15 1I
ZNF 0 36622 006362 0 43112 0 74557 -0 310B0 -004904 1 0 1350 08020 02466 0 0014 02595 08622
2 18 18 0 15 - 15 15 ---------- -1_
FEF 001413 -026846 0 13157 093257 -001512 -032131 2
middotmiddot--middotmiddotmiddotmiddotmiddot-middot-middot-middot---- -bull- --middotmiddotmiddot--middot middot----- - 1- 18 18 0 9 15 15 1
0956 0 2814 0 735B 00001 0 9573 0242 3
3
middots-1Fmiddot middot middot ~o 01 SOrmiddot-O 23405 - --- -------0--01367bull--o M7-n--0 0423P -0~31231-------------middot--middotmiddot-middot-middotmiddot-middot-middotmiddot-middot middot--middotmiddot-middotmiddot----middot------~----_ rmiddotmiddot 09433 0 3499 09722 00001 08808 02571 3
18 18 0 9 15 15 15imiddotmiddotmiddot CLF 008135 006398 -031045 -0 16144 -o 15703 0 15680
0 7483 0 8009 0 4162 o 5654 05762 0 5768 ---- ---o- - ------middot----- -middot ----middot --- 18 18 middot 9 15 15 15
NIF 0 23057 -023346 -o 14897 032692 028110 -0 22241 0 3573 03512 0 7021 02343 03102 0 4256
18 18 0 9 15 15 15 SF l 00000 066667 --- ----- middot-00573b - 0 1724~ -041658 052203
00000 00025 08835 0 5389 0 1224 00459 I 18 18 0 9 15 15 151middot I 1 N03 0 66667 1 00000 022436 -009255 -o 58411 079808
0 0025 0 0000 0 5617 0 7429 00222 0 0004 - o- t 5middot middot ---- middot - - -----middot- --- -- middot-middot middot- middot -middot-middot-----middot - ------~middot ~~1middotmiddot11 - 18 18 9 15 15
I I co
fi
0 0 0 0 0 0 0 bullbullbullNO -o 05736 0 22436 -- 1 00000 0 19817 -o 30163 0 58598 -middot---~-- middot5
0 8835 0 5617 00000 06093 0 4302 00973 bullmiddot 9 9 0 9 9 9 9
N02 0 17244 -o 09255 0 19817 100000 -009374 -0 16884 0 5389 0 7429 06093 00000 0 7397 0 5475
15 15 0 9 15 15 15 7
7
SAS 1527 WEDNESDAY MARCH 13 1985 33 STATION=7996
CORRELATION middotCOEFFIC IENTB middotmiddotmiddotPROB gt middotmiddotIR tmiddotmiddotUNDER-HORHOcO--NUHBER-middotOF--OBSERVATIONSmiddot------ --~
SF N03 co NO N02 03 S 2
03 -o 41658 -o 58411 -o 30163 -009374 1 00000 -o 56403 0 1224 0 0222 04302 o 7397 00000 00285
--~---middotmiddotmiddotmiddotmiddotmiddot -bullbullbull -bull--bull bull--bull -~ bullbull~bullr-- ~bull -----bull bullbullbullbullbull-bullbullbull _15 15 0 9 15 15 15
S02 0 52203 0 79808 0 58598 -0 16884 -0 56403 1 00000 0 0459 0 0004 0 0973 0 5475 00285 00000
15 15 0 9 15 15 15
i I fbull
-middot----~------ middotmiddot-middotmiddot--- --- - -middot-middotmiddot --- - ~-
APPENDIX IV aJMPLETE DATA SET FCR CONTRA COST A SEASONAL CXlMPOSITES
NOVEMBER 1979 - OCTCBER 1984
STATION 7430 = PITTSBLRG STATION 7433 = Ria-lMCllD STATION 7440 = aJNCXlRD PERIOD 801 = NOVEMBER 1979 - FEBRUARY 1980 PERIOD 802 = MARa-1 1980 - JUNE 1980 ETC
--
bullbull
SAS 1J 37 FRIDAY APRIL 5 1985
O 30 8 5 4 3 7433 811 76 0 43 12 2 10 1 499 8-tfrac14----~---e-2-l-------middot-6middot-9----middotmiddotmiddot-8middot5 ---- middotmiddotmiddot ----- 7433 813 55 020
I I ------------------------------------------middot---- STATIDNbull7430 ----------------------------------------------------------I
~ ODS 6fAHON PefH-aB-MAGS LEAB- 604 -Nea---OR~AfHGS BKF BAP lIQP ---GBR--18 TA98P TA90H fAIOl~RP TA9BNRM
J------middot--middot-middot--------i~-------- g1~ ~ 1 ____ g~- _g -----~ ~ gf ~1-----fri -t-- Z~ 3 7430 803 91 0 29 9 5 6 6 2 6 0 1 0 1 0 4 0 2 0 1 4 4 3 7 1 8 1 3 4 7430 811 85 039 94 122 55 04 05 24 12 10 88 41 45 17 1 74ao a12 69 o 11 1 ~ ----4-o a--1--~-1--0--t--G--4-middot-amp-a--o--t--t a 1 a -1 o -4----S------
e 6 7430 813 73 0 19 0 0 6 3 4 4 0 1 O l 0 3 0 2 0 1 5 1 3 2 2 2 0 9 bull 1 7430 821 58 035 57 94 59 03 05 18 09 13 132 97 80 32
----------------8-----7480 022--middot-middot-62--------018middotmiddotmiddot 5-----middot--4-amp-----2middot6middot---------0t------0middot1-----middot-0middotS-middotmiddotmiddot 02 -- 01 -4-5 ------4-t------- 86 16 9 7430 823 58 0 20 6 0 4 9 3 5 0 1 0 2 1 0 1 0 0 2 12 7 5 4 7 6 2 9 12 10 7430 831 50 0 25 4 9 8 8 5 0 0 5 0 6 33 22 2 4 113 60 73 3 7 11 74ao -aa2 44 o 11 ----5--0 2 s o 9 o o o e o 4 o 4 o o a 1 a o--- i a --o- -a----- 12 7430 833 58 017 65 52 13_ 00 01middot 05 02 02 148 74 62 17 13 7430 841 56 024 61 74 46 03 06 23 10 19 301 14B B9 32 - -------t-4-7400 042------51 --0 15 --- middot 6 0-- -4 2 2 9 --- middotmiddotmiddot 0-0 --- 0 t--- 0 8 - --0 2middot middot 0 2 middot-- Hr 1-----e--q----- -40- middot-- + 5 15 7430 843 65 014 23 01 01 06 05 01 124 81 39 17_I 11
18
10 ___ ~---~~~-~~~-_~--middot--~-----~~-----------middot------------- STATXON1117433 ___ ________ ____________ 4__~bull~~-bull--------------------middot--middot120
~ 1- ------aampa---middot--9-T-AHmiddot9ff---PEfH-6B- -- ---MASS-~ t-E-AB--------98-4-middot- - --NBB- ---- middotORAN-fes-- -ElltF--- -EIAP-- BGP---eeR-----Be---rA~8P-- -~--fW1-SM ~98NRP-----f-A98NRH middotmiddotmiddot 22f
23 16 7433 801 64 0 57 9 1 9 2 56 03 03 2 7 1 5 0 5 12 3 6 B 69 33
s o4 01 _ a4 aJL10- oA2e middot 3 1 0 1 0 1 0 4 0 3 0 l 4 0 middot bull 2 3 middot ltmiddot 12 3 l 0
26
27 5 4 0 3 0 3 2 5 l 4 0 7 12 1 6 B 3 6 7 0
middot9middot6----------0-middot1 middotmiddotbull O---l---e_--amp--middot---e--4-bullmiddot-ampbullt----------t4 2 -8--~8 0 -6--- - ---28( jbull~i 61 36 40 01 01 05 03 01 191 47 75 36 30 22 7433 821 63 0 43 5 2 6 9 5 1 0 4 0 5 2 6 1 3 1 3 11 3 5 7 6 8 3 2 -- 2a 14aa Bel ea o 22 6 s a a a 4 o 1 o 1 o 4 Q a o 1 cilth 4 9 a a ii 6if-
SI a --~- 823 4lt 020 65 29 35 01 01 11 12 01 33 126 26 06(__137
25 7433 831 51 0 32 7 0 52 58 06 09 48 3 5 17 14 7 66 7B 34 lJ
---20------~-----aa2 - -- -- -42 --- - o- tb- - --- -6 s-- - - 2 s 1 a--------middot---0--1 ---o t--------L t middot - Lt -- -o 2--middotmiddot-tt-~a--------middot4-----9middotmiddot-------s--s -- ------ t 6 -rJI 27 7433 833 55 018 76 38 19 01 01 07 03 03 147 60 64 19 -- 30 28 7433 841 52 0 28 6 6 5 1 5 9 0 4 0 7 3 3 1 4 2 0 27 4 15 2 9 4 3 9
7 -~~ -~~~~ ~~~ ~~ o i4 1 a a a a 1 o 1 o t o o o 4 o 2 i- s Hl o i 1 a a 0 U 2 1 0 1 0 1- 0 8 bull O 7 0 1 11 1 6 3 3 0 1 8
Ul3B 30
----------------------------------------------------------- STATIONbull7440 ---------------------------------------------------------l1bull 42
DBi -- 6T~HDN _ flERlG9 HASS ~Algt -694 Naa ~loF BAP BQP COR BO Ti1198P TA98H - TA98NRP TA91i1NRt4--43
44 31 _ 7440 801 73 069 77 112 107 06 13 41 19 33 48 12 77 24
40 ---------a2~--7-44a-------~-eo2---------ae----middot-- -o 28 3 7--- --- 2 7- --1 5-middot --o 1----- e--t- --0middot5-- --- o a o 1~~-1--~-----1---s------ao---------L-4 -- 33 7440 803 60 0 44 6 9 7 0 3 5 0 1 0 1 0 7 0 4 0 2 7 4 5 0 3 4 1 7 ltB 34 7440 811 90 073 74 101 105 06 12 39 18 19 144 75 90 16 6 7440 812 45 0 i24----4-4 4 6 a 4 0 middotl-----G l 09----amp--6----0 1 2 4 oil 5 14t--------------O-r-9------
36 7440 813 52 0 27 6 1 6 1 4 0 0 1 0 1 0 6 0 3 0 2 7 4 4 2 3 4 1 2 ~ 37 7440 821 61 050 44 83 107 06 15 40 18 29 55 35 30 17
88 7440- -- - 822 43 0 24 4 b 4 7 2 6 middot 0 1 -0 1 0 7 0 4 0 2 6 6 4 7 8 0 3 2 39 7440 823 39 0 24 4 9 4 4 2 9 0 1 ~- 1 1 1 1 1 0 1 17 1 5 4 6 1 7 M 40 7440 831 56 J42 41 69 106 10 c3 75 48 45 148 52 106 30
74 4 0 83a-----3d----O-t-7------4---4----8 --0-----------01----01-------h-l --- - L 2 --- --0 1---- -- -11 0 -- ------ b-0- middot--- -SA)-------11~-44-- 42 7440 833 45 020 55 50 12 01 01 07 03 02 178 77 84 2bulll
_ tor
----------------------------------------------- ---------------
__
bAl V J t-tHDAY At-tOL-
----------------------------------------------------------- STATI N-7440 ------------------------------------------ - - -----~--Qlii---4FfA+10N----~iA-HgtO----MAS6-----lEAO----- -t04-----NOa-------ORGANIGS----middot B~F------- BAP-- -BGfL COR ---IW -bull- -TA98fL--TA98t4- TA98NRP -middot- TAil8NHM Ibull
i~ 143 7440 041 so o 29 4 5 6 a a 1 o6 1 6 4 s 1 6 2 5 226 122 11 4 2 8 44 74lt10 842 asi -4---23--- 4-8----4-b------2-o--8--------9---0- l------0---8--------0 a--- 0-2------ 19-2-----12- o 4 6 ---t~o ------jb 45 7440 843 46 0 16 22 o 1 0 1 0 8 08 03 14 7 88 43 1 5 ~ r_--
1tl1-
1-1) i ~ I
middotmiddotmiddotmiddot-middot--bull-~-----middotmiddot-middot-- middot--a---middotmiddot------ ~--- -----middot-middot IltI
bull Ibull~Ilj rImiddoti---1 _ ~iI ~
----------- --bull~bull--bull-bull~~_m __ _____~-~--bullbullbullbull-
I~===~-=~----~~--1j i1_____ __ middotmiddot~middot~ - -~--~~-- ~- --~~ ----------===middot~~~-~-------- ------~- ---f_ i____ ___________ -----middot-- -middot - middotmiddot-middotmiddotmiddot
i lili
bullmiddotmiddot------- ----~----middotmiddot-middot
I middot1middot1
~ i -
------------------------- I bull
Imiddot I
ii middot
II
j I
I iI
--~----middot-middot- ---- -middot -middotmiddot--
APPENDIX V
LINEAR REGRESSION SLOPES OF COMPOSITE AEROSOL POLLUTANT DATA 1979-1984
YEAR VERSUS SEASON AND ANNUAL AVERAGE
Variable Season Slope P Value Variable Season Slope P Value
Pb Winter -008 lt0001- COR Winter 02 065
Spring -001 020 Spring 004 071
Summer -004 003 Summer 007 060
Annual -004 0001 Annual 009 050
N03 Winter -13 001 BZO Winter 03 015
Spring 008 077 Spring 002 016
Summer -05 019 Summer 002 028
Annual -05 005 Annual 01 013
TSP Winter -7 010
Spring -2 042
Summer -3 034
Annual -4 012
so4 Winter -09 016
Spring 005 063
Summer -06 024
Annual -05 011
Organics Winter -0l 036
Spring aa 099
Summer -04 021
Annual -02 042
BAP Winter 5 014
Spring aa 056
Summer aa 100
Annual 004 012
Slope different than zero at the P lt005 level of significance
11111i~~li~~IIII 07488