VISTAS Special Monitoring Stud

Carbon Analyses for PM2.5 and 

Patricia Brewer1, 

Johann Engelbrecht2, Roger Tanner3, 

Scott Reynolds

4, John Calcagni

5

1

VISTAS

2Desert Research Institute

3Tennessee Valley Authority

4South Carolina Department of Health and Environmental Co

5Environmental Protection A

gency
Presentation Objectiv

• VISTAS Data Analysis 

• Special Monitoring Studies Special Monitoring Studies

• Carbon Studies: C14 isotope, Positive 

Factorization, and Chemical Mass Ba
Areas with Poorest Visibility are similar to PM2.5 Non-attainm
BRIG1

DOSO1

JARI1

MACA1

SHEN1

CADI1

COHU1

GRSM1

HEGL1 LIGO1

MACA1

MING1

SHRO1

SWAN1

UPBU1

CACR1

ROMA1

SIPS1

Federa

Class 

CHAS1

OKEF1

SAMA1

BRET1 IMPR

EVER1
Average Extinction for 20% Haziest Day

N IMPROVE Al ith

2000-2004

New IMPROVE Algorithm 

250300200

(Mm -1) 

100150

Extinction ( 

50

100

0

SWAN

ROMA

OKEF

EVER

CHAS

SAMA

DOSO

SHEN

JARI

LIGO

SHRO

GRSM

COHU

SIPS

MACA

BRIG

BRET

MING

HEGL

UPBU

VISTAS coastal VISTAS inland non-VISTA

Sulfate dominates the 20% Haziest Days at VISTAS Class I 
Average Extinction for 20% Best Days

2000

-2004

New IMPROVE Algorithm

604050

M -1m)

30

Extinction (M 

1020

0

SWAN

ROMA

OKEF

EVER

CHAS

SAMA

DOSO

SHEN

JARI

LIGO

SHRO

GRSM

COHU

SIPS

MACA

BRIG

BRET

MING

HEGL

UPBU

VISTAS coastal VISTAS inland non-VISTAS

Sulfate also dominates the 20% Clearest Days at VISTAS Cla
Natural Conditions -- New IMPROVE Algorithm 

Left = B20%; Center = Average; Right = W20%

4050

*Breton based on 2001Q2-2002Q1 & 2002Q4-2003Q3 

)

2030

xt (Mm-1)

0

10

bex

0 
Monitoring Objective

Monitoring Objective

 Identify sources of organic carbon Identify sources of organic carbon

 Use high volume samplers with PM2.5 he

quartz filters at 5 sites

 S l ll t d A il 2004 Samples collec

t

e

d

April 2004

– M 2005 ay 2005

 Analyses by Desert Research Institute  Select 250 samples for carbon analysis (

Select 250 samples for carbon analysis (

50 samples per site including field and la

 Define carbon mass of each sample

 Ch t i i iti (GC/M

Charac

terize organic composition (GC/M

 Identify tracers of primary sources of carb

(Chemical Mass Balance and Positive MaFactorization)
Monitoring Objective

Monitoring Objective

 Identify sources of organic carbon Identify sources of organic carbon

 For same samples, characterize C1

isotope and ratio of modern to foss

 Analyses by Woods Hole Oceanograp

Institute’s National Oceanographic ScAccelerator Mass Spectrometry (NOSAccelerator Mass Spectrometry (NOS

 Sources of modern carbon: vegeta

emissions, wood burning, agricultu

burning, cooking

 Sources of fossil carbon: gasoline, 

oil
VISTAS Carbon Study Sites

Shenandoah

Mammoth Cave

Great Smoky Mtns. Raleigh

Cape Romain

CLASS 1 URBAN
Sources of Organic Ca

L Ld essons 

Learne

d

 Modern carbon fraction seldom <0 60 Modern carbon fraction seldom <0.60

usually >0.70 

 Higher modern carbon at forested site

Higher modern carbon at forested site

(GRSM and MACA) than coastal (ROurban 

( ) MILL

) sites

 Higher total carbon and higher total PM2.5 

urban site correspond to lower modern ca

 No clear seasonal trends in modern c

 Hypothesize that greater wood burning in 

months and greater vegetative emissions months and greater vegetative emissions 

spring/summer
Apr 2004 
Fraction Modern Carbon vs. Aerosol Carbo

Cape Romain, All Seasons 1.00

m

0.800.90

n Carbon, f

0.600.70

ction Moder

y = 0.045x + 0.556

R2 = 0.422 0.40

Fra 0.50c

0.30

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 

Aerosol C, 

μg/m

3

Fraction Modern Carbon vs. Aerosol Carbo

Great Smoky Mtns, All Seasons

1.10

y = 0.038x + 0.609

R2 = 0.1362

0.901.00

Carbon, fm

0.700.80

on Modern C

0.500.60

Fractio

0.300.40

0.00 1.00 2.00 3.00 4.00 5.00 6.00 

Aerosol Carbon , μg/m

3

Fraction Modern Carbon vs. Aerosol Carbo

Mammoth Cave, All Seasons

1 100.901.001.10

Carbon, fm

0.700.80

on Modern C

0.500.60

Fractio

0.300.40

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 

Aerosol Carbon , μg/m

3

Fraction Modern Carbon vs. Aerosol Carbo

Millbrook, All Seasons

0 901.001.10

arbon, fm

0.700.800.90

on Modern C

0.500.60

Fracti

0.300.40

0.00 2.00 4.00 6.00 8.00 10.00 

Aerosol Carbon , μg/m

3

Fraction Modern Carbon vs. Aerosol Carbo

Shenadoah, All Seasons

1.100.901.00

arbon, fm

0.700.80

on Modern C

y

= 0.054x

+ 0.514

0.500.60

Fractio

y 0.054x 0.514

R2 = 0.434

0.300.40

0 00 1 00 2 00 3 00 4 00 5 00 6 00 7 00 8 00 9 00 0.00 1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00 

Aerosol Carbon , μg/m

3
Monitoring Objective

Monitoring Objective

 Positive Matrix Factorization applied t

Positive Matrix Factorization applied t

cluster organic compounds. 

 Tracers identified fo

r

 Biogenic Emissions Vegetative Burn Gasoline emissions Diesel emissions Crude Oil (Commercial Marine seen at ROM

Crude Oil (Commercial Marine, seen at ROM

 Analyses incomplete: tracers still need to 

related back to total carbon to understan

relative importance
Vegetative burn

Biogenic EmissionsBiogenic EmissionsDiesel CrudeMotor vehicles




Monitoring Objective

Monitoring Objective

 Chemical Mass Balance anal

yses

 results to date from few samples analyze

Zheng, Ga Tech

 Ch i l k ( fil ) f i Chemical mar

kers 

(profiles

)

for primar

carbon sources:

 Wood Combustion Wood Combustion Gasoline emissions Diesel emissions Meat Cooking Meat Cooking Vegetative detritus Other Organic Matter (unidentified primary so

l d i)

plus secon

dary organics

)
GT-CMB R lt CMB Results

6.004.005.002 003.00

μg/m3

1.002.000.00

Diesel Gasoline Wood Combustion Meat Cooking Vegetative Detritus 
Carbon Source Attribu

Lessons Learned

 CMB Results from samples analyz

CMB Results from samples analyz

Mei Zheng, Ga Tech

 In A

p p ril sam

ples from all sites, unide

component is largest fraction (>70%)

 Likely secondary, likely biogenic 

 W d b ti i l t id tifi 

Woo

d com

bustion is larges

t identifi

e

component in Jan samples, all sites

 Gasoline higher in Jan than Apr sam

Gasoline higher in Jan than Apr sam

 Diesel at all sites in Apr, not Jan sa
Carbon Source Attribu

Lessons Learned

 CMB analyses together with C14 CMB analyses together with

C re

re

indicate that modern carbon is moimportant than fossil carbon at Cla

areas and urban area sampled.

 Little seasonal variability in modern c

 wood burning vs biogenic

 Still need integration to understand s

contributions
Next Steps Next Steps

 Relate organic tracers used as PMF fact

larger population of organic compounds 

 Complete CMB organic analyses all sam

 Relate organic profiles to measured carb Integrate results with C14 analyses  Interpret source attribution for organic ca Integrate results with SOA production in 

CMAQ/CAMx air quality models CMAQ/CAMx air quality models

 Finalize project reports  Submit manucript for publication

Submit manucript for publication