St. Louis - Midwest Supersite Fine Particulate Matter Field Campaign at Reserve, KS

Neil D. Deardorff

Scott A. Duthie

Jay R. Turner

Environmental Engineering Program

Washington University in St. Louis

Jeffery D. Reifschneider

Environmental Department

Sac and Fox Nation of Missouri

National RPO Work Groups Meeting

St. Louis, MO

November 4-6, 2003

Introduction• As part of the St. Louis – Midwest Supersite program, a movable

measurement platform was instrumented and deployed at two rural locations:– Rural southeastern Missouri, approximately 100 km south of

St. Louis– Rural northeast Kansas, collocated with an IMPROVE

protocol site established in Summer 2002 • Measurement Objectives

– Complement sustained measurements in East St. Louis (IL) by providing urban/rural contrast

– Explore aerosol climatology in the CENRAP domain to support regional haze program development and implementation

• Measurement Periods– August to November, 2001 in Park Hills, MO– August to December, 2002 in Reserve, KS

Reserve, KS

CENRAP domain

Park Hills, MO

Monitoring Locations

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sampling location

Reserve, Kansas

Measurements Summary - Reserve

• St. Louis - Midwest Supersite movable platform deployed at Reserve, KS, in collaboration with the Sac & Fox Nation of Missouri

• Hourly-average (or finer) data for: meteorology; and PM-2.5 mass, nitrate, sulfate, aethalometer black carbon, and nephelometer light scattering

• Daily 24-hour average data for: PM precursor gases; PM-10 mass; and PM-2.5 mass, ions, carbon, and metals

• Two six-week measurement periods

– August 24 to October 5, 2002 (continued to October 23)

– November 18 to December 31, 2002

– selected semicontinuous monitors operated during the six-week interim period

• Emphasis on Reserve, KS measurements…– Anatomy of a regional sulfate event– Potential evidence for long-range transport of smoke– Field application of anhydrous ammonia

• Brief results from the Park Hills, MO measurements…– Comparisons of components coupled and uncoupled

with St. Louis data

Features of this Presentation

Anatomy of a Regional Sulfate Event

• Four tools to demonstrate the event structure…– Semicontinuous sulfate measurements in Reserve and St.

Louis– daily 24-hour integrated sulfate in Reserve and St. Louis– 1/3 day 24-hour integrated sulfate at the IMPROVE network

sites– Naval Research Laboratory (NRL) model predictions

(b)

8/27

8/28 8/29

8/30 8/31

9/1

9/2

9/3

air mass back trajectories from NOAA/ARL HYSPLIT model

Regional IMPROVE Data and Air Mass Back Trajectories

August 24

August 27

August 30

• Harvard School of Public Health (HSPH) sulfate method

– 54% conversion efficiency during this deployment as determined by comparisons to daily 24-hour integrated filter sulfate by the Harvard-EPA Annular Denuder System (HEADS)

Semicontinuous Sulfate in Reserve

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300

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/28

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/29

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/31

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PM

-2.5

Su

lfate

Co

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atio

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m g/m

3 )

Reserve, daily average

Reserve, hourly average

St. Louis, hourly average

PM-2.5 Sulfate Event

Top: Predicted sulfate from the Naval Research Laboratory (NRL) NAAPS model. Bottom: Sulfate measured at an urban site (St. Louis) and rural site (Reserve).

On August 28 the northwestern edge of the high sulfate domain includes St. Louis but not Reserve, while on August 31 the high sulfate domain extends west to Reserve.

8/28/02, 1200 CST 9/1/02, 0000 CST

Supersite versus IMPROVE ComparisonsPM-2.5 Sulfate: August 24 – November 30, 2002

all concentrations in mg/m3

[IMPROVE] = (0.97 +/- 0.04) x [HEADS]

R2 = 0.987N = 19 (August - November 2002)

colocated precision = 0.23 mg/m3

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0 2 4 6 8 10 12

HEADS PM-2.5 Sulfate

Imp

rove

PM

-2.5

Su

lfate

• Excellent agreement between HEADS and IMPROVE sulfate data

• Intercept statistically indistinguishable from zero at 95% CL

• Slope statistically indistinguishable from unity at 95% CL

Supersite versus IMPROVE Comparisons PM-2.5 Nitrate: August 24 – November 30, 2002

• Excellent agreement between HEADS and IMPROVE nitrate data (note scales are factor of two smaller than sulfate scatter plot)

• Intercept statistically indistinguishable from zero at 95% CL

• Slope statistically indistinguishable from unity at 95% CL

all concentrations in mg/m3

[IMPROVE] = (1.00 +/- 0.09) x [HEADS]

R2 = 0.934N = 19 (August - November 2002)

colocated precision = 0.21 mg/m3

0

1

2

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0 1 2 3 4 5 6

HEADS PM-2.5 Nitrate

Imp

rove

PM

-2.5

Nitr

ate

PM-2.5 Sulfate and Associated Ammonium:August 28 – October 9, 2002 (Period #1)

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PM

-2.5

Su

lfate

, mg

/m3

0.0

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1.0

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3.0

mo

les

am

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ulfa

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sulfatemoles ammonium per mole sulfate (nitrate corrected)

PM-2.5 Sulfate and Associated Ammonium:November 18 – December 31, 2002 (Period #2)

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PM

-2.5

Su

lfate

, mg

/m3

0.0

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1.0

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2.0

2.5

3.0

mo

les

am

mo

niu

m p

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mo

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ulfa

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sulfatemoles ammonium per mole sulfate (nitrate corrected)

Long-Range Transport of Smoke: Do Fires Show up in the Reserve data?

• Instances of coupled high concentrations of aethalometer black carbon (BC) and sulfate observed

• During such periods, air masses back trajectories originate in the southeastern U.S. pass and pass nominally through Arkansas before arriving in Reserve, KS.

– NRL model qualitatively consistent with these observations when fires are reported in MODIS (database from which model is developed)

• Large number of fires in Arkansas during the early part of September from Arkansas Fire Reports which are not reported in MODIS

– Satellite imagery detects possible smoke haze

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20

9/4/02 9/5/02 9/6/02 9/7/02 9/8/02 9/9/02 9/10/02 9/11/02 9/12/02 9/13/02 9/14/02 9/15/02

Su

lfate

Co

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/m3

)

0

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Bla

ck C

arb

on

Co

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ntr

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n (m g

/m3 )

HSPH Sulfate

Aethalometer Black Carbon

Sep

t. 5

: C

oupl

ed

Sep

t. 1

1:

Dec

oupl

ed

Carbon-Sulfate Coupling

Sep

t. 1

0: C

oupl

ed

NRL Model Predictions• On September 5 trajectories

and prediction maps qualitatively show a relation to transport from the Southeast.

Sulfate

Smoke

Air mass back trajectory for noon CST on September 5

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10

15

20

9/4/02 9/5/02 9/6/02 9/7/02 9/8/02 9/9/02 9/10/02 9/11/02 9/12/02 9/13/02 9/14/02 9/15/02

Su

lfate

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/m3

)

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arb

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/m3 )

HSPH Sulfate

Aethalometer Black Carbon

Sep

t. 5

: C

oupl

ed

Sep

t. 1

1:

Dec

oupl

ed

Carbon-Sulfate Coupling

Sep

t. 1

0: C

oupl

ed

Air Mass Back Trajectories and Carbon-Sulfate Coupling

Sept. 10: CARBON & SULFATE COUPLED

Sept. 11: CARBON & SULFATE

DECOUPLED

September 10: Satellite-Observed Smoke

• Satellite imagery shows possible smoke haze• Large number of fires in Arkansas during this period according to Fire Reports from the

State of Arkansas (need to check other states)

Haze

Reserve, KS

SeaWiFS

Sept 10

Ambient Ammonia

• Anhydrous ammonia application observed in the late fall / early winter, coinciding with large spikes in ammonia at the monitoring site (daily 24-hour integrated samples from the Harvard-EPA Annular Denuder System, HEADS)

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08/27/02 09/10/02 09/24/02 10/08/02 10/22/02 11/05/02 11/19/02 12/03/02 12/17/02 12/31/02

Date

24-h

our

Inte

grat

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mm

onia

Con

cent

ratio

n (p

pb)

Field Operator noted on November 18 that anhydrous ammonia application occurred at a field north of the site.

Study Period One Study Period Two

Urban/Rural Contrast Measurements

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08/17/01 08/27/01 09/06/01 09/16/01 09/26/01 10/06/01 10/16/01 10/26/01 11/05/01 11/15/01 11/25/01

Con

cent

ratio

n (u

g/m

3)

Park Hills

East St. Louis

• Deployment at Park Hills, MO, which is approximately sixty miles south of the City of St. Louis and the East St. Louis, IL, St. Louis – Midwest Supersite core monitoring location

• Gaseous species and particulate matter components exhibit varying degrees of coupling, ranging from highly coupled for sulfate to highly decoupled for elemental carbon and gaseous ammonia

Park Hills & East St. Louis Time Series

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08/17/01 08/27/01 09/06/01 09/16/01 09/26/01 10/06/01 10/16/01 10/26/01 11/05/01 11/15/01 11/25/01

Con

cent

ratio

n (u

g/m

3)

Park Hills

East St. Louis

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3.5

4.0

08/17/01 08/27/01 09/06/01 09/16/01 09/26/01 10/06/01 10/16/01 10/26/01 11/05/01 11/15/01 11/25/01

Con

cent

ratio

n (u

g/m

3)

Park Hills

East St. Louis

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2.0

2.5

08/17/01 08/27/01 09/06/01 09/16/01 09/26/01 10/06/01 10/16/01 10/26/01 11/05/01 11/15/01 11/25/01

Con

cent

ratio

n (p

pb)

Park Hills

East St. Louis

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08/17/01 08/27/01 09/06/01 09/16/01 09/26/01 10/06/01 10/16/01 10/26/01 11/05/01 11/15/01 11/25/01

Co

nce

ntr

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pp

b)

Park Hills

East St. Louis

Ammonia Nitric Acid

Elemental Carbon Organic Carbon

Acknowledgements• Washington University in St. Louis

– Stefan Falke• CENRAP Monitoring Work Group

– Ray Bishop and Brandon Krogh, Co-Chairs

• USEPA

– Mike Davis, Project Officer – Mike Jones, Project Officer

• Harvard School of Public Health

– Petros Koutrakis and Mark Davey

• University of Wisconsin- Madison

– Jamie Schauer, Min-Suk Bae and Jeff DeMinter

• Desert Research Institute

–Judy Chow, John Watson, Matt Gonzi

Future Plans• Submit validated data to VIEWS

• Further investigate observed features observed in the data towards developing a conceptual model for aerosol climatology in Northeast Kansas to support regional haze planning

• Execute and report out on the data analysis plan elements

The research described in this presentation has been funded in part by the United States Environmental Protection Agency through cooperative agreement R-82805901-0 to Washington University. It has not been subjected to the Agency's required peer and policy review and therefore does not necessarily reflect the views of the Agency and no official endorsement should be inferred.