constraints of asian voc sources from gome hcho observations tzung-may fu, paul i. palmer, dorian s....
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CONSTRAINTS OF ASIAN VOC SOURCESCONSTRAINTS OF ASIAN VOC SOURCESFROM GOME HCHO OBSERVATIONSFROM GOME HCHO OBSERVATIONS
Tzung-May Fu, Paul I. Palmer, Dorian S. Abbot, Daniel J. JacobTzung-May Fu, Paul I. Palmer, Dorian S. Abbot, Daniel J. JacobAtmospheric Chemistry Modeling Group, Harvard UniversityAtmospheric Chemistry Modeling Group, Harvard University
Kelly V. Chance and Thomas KurosuKelly V. Chance and Thomas KurosuHarvard/Smithsonian Center for AstrophysicsHarvard/Smithsonian Center for Astrophysics
M.J. Pilling and J. Stanton (U. Leeds); A. Guenther, C. Wiedinmyer (NCAR); M.J. Pilling and J. Stanton (U. Leeds); A. Guenther, C. Wiedinmyer (NCAR); B. Barletta (UC Irvine)B. Barletta (UC Irvine)
OutlineOutline
I. Vegetation representation
- AVHRR LAI
- MEGAN inventory for biogenic VOCs
II. Constraints on East Asian VOC emissions
- GOME information
- TRACEP information
III. Summary
AVHRR Leaf Area Index 1982 – 2000AVHRR Leaf Area Index 1982 – 2000
AVHRR 10 day maximum NDVI
8km monthly LAI
0.5deg monthly LAI
Model grid monthly LAI
Myneni et al. (1997)
Landmap and Climatology T & precip.
NPP
0.5deg monthly LAI
Model grid monthly LAI
+/- 20%
AVHRR Leaf Area Index ValidationAVHRR Leaf Area Index Validation
Buermann et al. (2002)Dust mobilization and dry deposition also sensitive to LAI
AVHRR Leaf Area Index Interannual VariabilityAVHRR Leaf Area Index Interannual Variability
Buermann et al. (2002)
July + August (40-50N)
April + May (40-50N)
Modeling the terrestrial biosphere
April Sep
LA
IPAR – direct and diffuse (GMAO)
AVHRR LAI
Canopy model (Guenther 1995)
Alt
itu
de
Emission
Temperature:
Instantaneous (G95)
15-day history avg
Fixed base emission factors (Guenther 2004)
Emissions
Courtesy Paul Palmer
GEOS3, GEOS4
Model of Emissions of Gas and Aerosols from Model of Emissions of Gas and Aerosols from Nature (MEGAN) INVENTORYNature (MEGAN) INVENTORY
Emission rate = AEF × MEF × DEF × HEF
Alex Guenther and Christine Wiedinmyer (NCAR)
Leaf area
Leaf age
Light
Temperature
Canopy attenuation
T history
World ecoregion map
EF by ecoregion
AVHRR land cover
(plant type fraction)
MEGAN INVENTORYMEGAN INVENTORY
Guenther et al. (manuscript in preparation)
GEIA [Tg C/yr] MEGAN [Tg C/yr]
Isoprene 352.2 367.9
Monoterpenes 147.7 97.6
MBO - 1.16
Acetone (87.76) (87.76)
PRPE (10.07) (10.5)
GEIA [Tg C/yr] MEGAN [Tg C/yr]
Isoprene 12.31 3.99
Monoterpenes 4.59 1.88
(OVOC)* 13 9.1
Not implemented. From Klinger et al. [2002].
Chinese emissions:
Compare to Anthro+BB NMVOC emission = 17.4 Tg/yr
Global emissions:
BVOC EMISSION INVENTORYBVOC EMISSION INVENTORY
MEGAN
• GEOS3, GEOSS• Global isoprene 367.9 Tg C/yr• Latest emission factors• AVHRR land map and lai
• AEF must be computed offline for land use change studies
GEIA
• GEOS1, GEOSS, GEOS3, GEOS4• Global isoprene 352.2 Tg C/yr• Olson (1982) land map
• More flexibility for land use change studies
RELATING HCHO COLUMNS TO VOC EMISSIONRELATING HCHO COLUMNS TO VOC EMISSION
VOCi HCHOh (340 nm), OHoxn.
k ~ 0.5 h-1
Emission Ei
smearing, displacement
In absence of horizontal wind, mass balance for HCHO column HCHO:
i ii
HCHO
y E
k
yield yi
… but wind smears this local relationship between HCHO and Ei depending on the lifetime of the parent VOC with respect to HCHO production:
Local linear relationshipbetween HCHO and E
VOC source Distance downwind
HCHOIsoprene
-pinenepropane
100 km
CourtesyP.I. Palmer (Harvard)
EVALUATING GOME ISOPRENE EMISSION ESTIMATES EVALUATING GOME ISOPRENE EMISSION ESTIMATES vs. PROPHET IN SITU FLUX MEASUREMENTS (2001)vs. PROPHET IN SITU FLUX MEASUREMENTS (2001)
Also shown are local MEGAN isoperene emission inventory values
P.I. Palmer (Harvard), S.N. Pressley and B. Lamb (WSU), A. Guenther and C. Wiedinmyer (NCAR)
GOME HCHO COLUMNS OVER EAST ASIA (1996-2001)GOME HCHO COLUMNS OVER EAST ASIA (1996-2001)
Relationship to VOC emissions far more complex than for N. America. Biomass burning, isoprene, anthropogenic VOCs, direct HCHO emission all contribute; need multivariate regression
APRJAN
FEB
MAR
MAY
JUN
JUL
AUG
SEP
OCT
NOV
DEC
GOME HCHO COLUMNS OVER EAST ASIA (1996-2001)GOME HCHO COLUMNS OVER EAST ASIA (1996-2001)
APR
MAY
JUN
JUL
AUG
SEP
NC
CCWC
SC
0% 20% 40% 60% 80% 100%
Changchun
BengbuHefei
BeijingLangfang
QinghuangdaoShijiazhunag
TangshanNanyangXinyang
XuchangZhengzhou
SuizhouJiningJinan
QingdaoZouchengShanghai
TaiyuanWeinan
ChongqingLanzhouGuiyang
YinchuanKunming
HaMiUrumqi
Golmud
AnqingShishouWuhanXiantao
ChangdeChangsha
QiyangShaoyang
ZhangjiajieJi'an
JingdezhenJiujiang
LinchuanNanchang
BeihaiGuilin
HangzhouTaihu
Wenzhou
Ethane
Propane
ALK4
Ethene
PRPE
Benzene
Toluene
Xylene
Isoprene
VOC CONTRIBUTIONS TO HCHO PRODUCTION VOC CONTRIBUTIONS TO HCHO PRODUCTION IN CHINESE CITIES (JAN-FEB 2001)IN CHINESE CITIES (JAN-FEB 2001)
Ethane 0.3 % Benzene 0.4 %
Propane 0.3 % Toluene 2.4 %
ALK4 5.1 % Xylene 20.2 %
Ethene 19 % Isoprene 8.2 %
PRPE 43 %
B. Barletta (UCI), T.-M. Fu (Harvard)
Vehicle-generated xylenes could make a large contribution to HCHO columns
NC
CC
WC
SC
Streets inventory for East AsiaStreets inventory for East Asia
Klimont et al. [2002]
M is c e l la n e o u sW a s te d is p o s a lT ra n s p o r tP a in t u s eS o lv e n t u s eC h e m ic a l in d u s t r yE x t ra c t io n a n d p ro c e s s in gS ta t io n a ry c o m b u s t io n
Eth
an
e
Pro
pa
ne
Bu
tan
es
Oth
er
alk
an
es
Eth
en
e
Pro
pe
ne
Oth
er
alk
en
es
Eth
yne
Be
nz
en
e
To
lue
ne
Oth
er
aro
ma
tic
s
Fo
rma
lde
hyd
e
Oth
er
ald
eh
yde
s
Ke
ton
es
Ha
loca
rbo
ns
Oth
er
sp
ec
ies
Tota
l/1
0
050
010
0015
0020
002
500
NM
VO
C a
nth
rop
og
en
ic e
mis
sio
n, G
g /
ye
ar
GOME r2
0.48
0.47
0.32
Uncertainty
+/- 130%
VOC / CO emission ratio in Chinese citiesVOC / CO emission ratio in Chinese cities
Streets et al. [2001]
Obs. Model
emission
Obs. / Model
emission Ethene NC 1.61e-2 0.66e-2 7.84e-2 0.084 Ethene CC 1.44e-2 0.45e-2 1.17e-2 0.38 Ethene WC 1.39e-2 0.45e-2 0.68e-2 0.66 Ethene SC 1.82e-2 0.51e-2 2.03e-2 0.25
PRPE NC 1.19e-2 0.38e-2 5.79e-2 0.066 PRPE CC 9.88e-3 2.61e-3 8.04e-3 0.32 PRPE WC 9.98e-3 3.00e-3 4.90e-3 0.61 PRPE SC 1.30e-2 0.45e-2 1.45e-2 0.31
XYLE NC 1.41e-3 0.78e-3 6.87e-3 0.11 XYLE CC 1.28e-3 1.99e-3 1.05e-3 1.89 XYLE WC 1.25e-3 1.52e-3 0.62e-3 2.45 XYLE SC 1.16e-3 2.70e-3 1.29e-3 2.09
ISOP NC 0 9.88e-5 0 - ISOP CC 0.16e-4 1.57e-4 0.13e-4 12.07 ISOP WC 6.60e-4 1.58e-4 3.22e-4 0.49 ISOP SC 5.73e-4 2.90e-4 6.45e-4 0.45
Obs data: B. Barletta UC Irvine
Streets ETHE/CO 3x too high
XYLE/CO 2x too low
SimulationSimulation
• GEOS3 2x2.5 2001
• East Asia: Streets inventory [2001] including ETHE, XYLE and direct HCHO emission
• C2H6: Xiao et al. [2004]
• CO correction: Heald et al. [2004]
• NOx correction: Wang et al. [2004b]
• Anthropogenic seasonality (FF+BF): Streets et al. [2003]
• Biomass burning seasonality: Duncan et al. [2003] + Heald et al. [2003]
• MEGAN inventory (AVHRR LAI)
• ETHE, XYLE, MONX chemistry
CC22HH44 chemistry chemistry
Vereecken and Peeters [1999]
Orlando et al. [2003]
Lifetime HCHO Yield per C
OH 6 hours 0.89
O3 6.8 days 0.57
NO3 110 days
Assuming midmorning summer conditions: [OH] = 5 × 106 molecule cm-3, [O3] = 40 ppb, nighttime average [NO3] = 5 × 108 molecules cm-3, and a temperature of 298 K.
AromaticsAromatics
0 1 2 3 4 5 6 7 8 9 100.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
HC
HO
YIE
LD P
ER
C R
EA
CT
ED
days
NOX = 1PPB
NOX = 100 PPTTOLUENE
0.18 per C
J. Stanton and M. Pilling
Bloss et al. [2004]
MCM v3.1
OH = 9.9 h
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 200.00
0.05
0.10
0.15
0.20
0.25
0.30
HC
HO
YIE
LD P
ER
C R
EA
CT
ED
days
NOX = 1 PPB
NOX = 100 PPT
MXYL
0.26 per C
MCM v3.1
OH = 2.4 h
m-xylene
toluene
High HCHO and GLXY yield from aromatic hydrocarbons also observed by Volkamer et al. [2001].
HCHO underestimated in MCM
Xylene removal underestimated in MCM
Measurements show rapid SOA formation
TRACEP: Chinese outflow TRACEP: Chinese outflow [30-60N, 120-150E] z < 2km, [CO] < 400 ppbv[30-60N, 120-150E] z < 2km, [CO] < 400 ppbv
OBS
Model w/ ETHE, XYLE
Model w/o ETHE, XYLEModel only 23% of observation
TRACEP: Chinese outflow TRACEP: Chinese outflow [30-60N, 120-150E] z < 2km, [CO] < 400 ppbv[30-60N, 120-150E] z < 2km, [CO] < 400 ppbv
OBS
Model w/ ETHE, XYLE
Model ETHE/CO 3x too high
HCHO sources independent of ETHE contribute ~50%
Model XYLE/CO 3x too high
Direct HCHO sources from transportation?Direct HCHO sources from transportation?
Kolb et al. [2004]
Streets emission
HCHO / CO2 =
4 x 10-7 – 4 x 10-5 [mole/mole]
Mexico City
2 x 10-4 [mole/mole]Boston
3 x 10-5 [mole/mole]
HC
HO
(p
pb
)
CO2 (ppm)
SUMMARYSUMMARY
• From in-situ measurements:
• Short-lived anthropogenic VOCs such as alkenes and xylenes contributes > 80% to local HCHO production, and > 25% to HCHO VC
• Ethene/CO emission may be overestimated by factors of 3-4 in parts of China
• Xylene/CO emission may be underestimated by factors of 2-2.5
• Preliminary model and TRACEP comparisons agree with in situ measurements
• Possibile direct HCHO source independent of ethene emissions
• In progress: multivariate regression to evaluate relative contribution from different sources
BACKUPBACKUP
1 x 1
2 x 2.5
4 x 5
GOME (launched Apr 1995)
Nadir viewing
Global coverage in 3 days
320 km x 40 km
O3, NO2, HCHO, etc
Jul 1995 to Dec 2003
SCIAMACHY (launched Mar 2002)
Nadir/limb
Global coverage in 3 days
60 km x 30 km
O3, NO2, HCHO, CO, CO2, CH4, etc
A. Richter, IUP U Bremen
OMI (launched Jul 2004)
Nadir viewing
Global coverage in 1 day
24 km x 13 km
O3, NO2, HCHO, etc
1 x 1
2 x 2.5
4 x 5
Monthly mean LAI (AVHRR/MODIS)
MEGAN (isoprene)Canopy model
Leaf areaLeaf age
Temperature historyBase factors
MODEL BIOSPHERE
GEIAMonoterpenes
MBOAcetoneMethanol
GEOS-CHEMGlobal 3D CTM
PAR, T
Emissions
Global 3-D Modeling Overview•Driven by NASA GMAO met data
•2x2.5o resolution/30 vertical levels
•O3-NOx-VOC-aerosol chemistry
INVERTING HCHO COLUMN DATA FOR ISOPRENE EMISSIONINVERTING HCHO COLUMN DATA FOR ISOPRENE EMISSIONGOME slant columns (July 96)
GOME vertical columns (July 96)
Air Mass Factor
EISOPRENE =(1/S)HCHO
GOME isopreneemission inventory
GEOS-CHEMCTM
GOME/OMIsensitivity
HCHO vmrS
igm
a co
ord
inat
e
validationWith HCHOsurface airobservations
with GEIAisoprene emissioninventory
with GOMEisopreneemission inventory
Palmer et al. [2001, 2003]
EISOPRENE
HC
HO
co
lum
n
non- isoprene contribution
Southeast U.S.
slope S
Observed HCHO, ppb
Mo
del
HC
HO
, p
pb
WHAT DRIVES GOME HCHO TEMPORAL VARIABILITY WHAT DRIVES GOME HCHO TEMPORAL VARIABILITY OVER SOUTHEAST U.S. DURING MAY-SEPTEMBER?OVER SOUTHEAST U.S. DURING MAY-SEPTEMBER?
P.I. Palmer (Harvard)
Monthly mean GOME HCHO vs. surface air temperature;MEGAN parameterization shown as fitted curve
GO
ME H
CH
O C
olu
mn
[10
16 m
ole
c
cm
-2]
Southeast US average 32-38N; 265-280W
YEAR-TO-YEAR VARIABILITY OF GOME HCHO OVER SOUTHEAST U.S.YEAR-TO-YEAR VARIABILITY OF GOME HCHO OVER SOUTHEAST U.S.Amplitude and phase are highly reproducible
P. I. Palmer (Harvard)
Biogenic VOC emissions: Biogenic VOC emissions:
a pathway of biosphere – atmosphere interactiona pathway of biosphere – atmosphere interaction
B io s p h e re
A tm o s p h e re
H u m a n a c tiv it ie s
V O C s
O , C H , C O ,o r g a n ic a e ro s o ls
3 4
R a d ia t io n ,Te m p e ra tu re ,P re c ip i ta t io n ,C lo u d c o v e r,C O 2
GHG, aerosols
Changing landuse, hydrology
Fertilization