COMPARISON

OF VOC:CO RATIOS IN MULTIPLE REGIONS OF THE SOUTH COAST AIR BASIN

Eric Praske Pitzer College 13 Student Airborne Research Program 2012 August 8, 2012

VOCs : The Bad and The Bad

Several VOCs are toxins
Using VOC data to evaluate carcinogenic risk
Benzene, 1,3-butadiene, formaldehyde, acetaldehyde

Photochemical pathways O3

Fate of VOCs in SoCAB

PAMS VOCs, NOx, Ozone

Source: Prof. Don Blake of UC Irvine, The importance of VOCs in local and regional air quality, SARP 2012

Source: Dept. of Chemistry, Washington State University at St. Louis

MulRple Air Toxics Exposure Study

Toxic Air Contaminants to be Monitored in MATES

1,3-Butadiene Acetaldehyde Arsenic Benzene Toluene m,p, and o-Xylenes Ethylbenzene Beryllium Cadmium Carbon Tetrachloride Vinyl Chloride

Chloroform Formaldehyde Hexavalent Chromium Lead Manganese Methylene Chloride Naphthalene Nickel Perchloroethylene Polycyclic AromaRc Hydrocarbons (PAHs) Trichloroethylene

Other Substances to be Monitored PM10 PM2.5 Ultra Fine ParRcles Elemental Carbon Organic Carbon Total Carbon Black Carbon Diesel PM

Previous Studies
MATES III 2004-2006 NMHCs in 28 United States ciRes (2008) Determining contribuRons of automoRve exhaust and evap. VOC emissions in Riverside (2009) Weekend enhancement of ozone producRon using VOC/NOx (2012)

The Big Picture

A Year-to-Year Comparison by Month

Benzene Decline in SoCAB Mt. Wilson, ARCTAS, CALNEX, SARP 3-4

0.9 Benzene (pptv) : CO (ppbv) 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 May-07 May-10 Jun-08 Jun-10 Jun-11 Jun-12

SoCAB with MATES LocaRons Overlaid

MATES III Assessment

Source: MATES III, Final Report 2008, South Coast Air Quality Management District.

Region SelecRon

Note: MATES IV sampling locaRons indicated by yellow pins

Region SelecRon

Note: MATES IV sampling locaRons indicated by yellow pins

Region SelecRon

Note: MATES IV sampling locaRons indicated by yellow pins

Region SelecRon

Note: MATES IV sampling locaRons indicated by yellow pins

CALNEX Regional Comparison

Benzene:CO
Benzene(pptv) : CO (ppbv)

Other AromaPcs:CO
Benzene(pptv) : CO (ppbv)

0.8 0.6 0.4 0.2 0 R1 (0.81) R2 (0.92) R3 (0.97) R4 (0.95)

3 2 1 0 R1 (0.75) R2 (0.70) R3 (0.83) R4 (0.76)

Acetaldehyde:CO
Benzene(pptv) : CO (ppbv) Benzene(pptv) : CO (ppbv)

C2Cl4:CO
0.2 0.15 0.1 0.05 0 R2 (0.50) R3 (0.77) R4 (0.57)

8 6 4 2 0 R1 (NC) R2 (NC) R3 (NC)

R1 (0.70) R4 (NC) r2 values for correlaPon plots in ()

PAMS for May-June 2010

PAMS Benzene:CO
7 6 Benzene (pptC) : CO (ppbv) 5 4 3 2 1 0 R2 R3 R4

Decreases in Riverside/San Bernardino

Suggests oxidaRon in the ozone formaRon pathway ParRcle phase conversion
12.5% vs. 2-5% at the coast

OH radical oxidaRon of aromaRcs forming carbonyls (e.g. benzaldehyde)

Regions by Year
Data represents June only
Benzene:CO
Region 3
Benzene (pptv) : CO (ppbv)

1 0.8 0.6 0.4 0.2 0

Region 1

Region 2

Region 4

2008 Region 1

2010

2008 Region 2

2010

2011

2008 Region 3

2010

2008 Region 4

2010

2012

Other AromaPcs:CO

Benzene (pptv) : CO (ppbv)

3 2 1 0

2008

2010

2008

2010

2011

2008

2010

2008

2010

2012

Contd
0.16 0.14 0.12
Benzene (pptv) : CO (ppbv)

Region 1

Region 2

C2Cl4:CO

Region 3

Region 4

0.1 0.08 0.06 0.04 0.02 0 2008 2010 2008 2010 2011 2008 2010 2008 2010 2012

Rickys Program DAN

Future Work
Beger characterizaRon of raRos by lower elevaRon ights Enhanced ozone eect parRcularly true for this region or can this be extended? Need for airborne campaigns outside of summer season

References
Airborne and ground-based observaPons of a weekend eect in ozone, precursors, and oxidaPon products in the California South Coast Air Basin. Pollack, I. B., et al., Journal of Geophysical Research 2012, 117. Air Quality Model EvaluaPon Data for Organics. Bulk Chemical ComposiPon and Gas/ParPcle DistribuPon Factors. Ma]hew P. Fraser, Daniel Grosjean, Eric Grosjean, R. A. Rasmussen, and Glen R. Cass, Environmental Science & Technology 1996, 30 (5), 1731-1743. Carbonyl atmospheric reacPon products of aromaPc hydrocarbons in ambient air. Genevieve Obermeyer, Sara M. Aschmann, Roger Atkinson, Janet Arey, Atmospheric Environment 2009, 43 (24), 3736-3744. Diurnal and Seasonal Variability of Gasoline-Related VolaPle Organic Compound Emissions in Riverside, California. Drew R. Gentner, Robert A. Harley, Angela M. Miller, and Allen H. Goldstein, Environmental Science & Technology 2009, 43 (12), 4247-4252. Updated Maximum Incremental ReacPvity Scale And Hydrocarbon Bin ReacPviPes For Regulatory ApplicaPons. Bill Carter, CARB, 2009. Graphic. Dept. of Chemistry, Washington State University at St. Louis. Prof. Don Blake of UC Irvine, The importance of VOCs in local and regional air quality, SARP 2012. MATES III, Final Report. South Coast Air Quality Management District, 2008. US Environmental ProtecRon Agency. Air Quality System Data Mart [internet database] available at hgp://www.epa.gov/gn/airs/aqsdatamart. Accessed August 2012.

Acknowledgements
Greg Harg Prof. Don Blake All of SARP and especially WAS Rowland-Blake group for analysis Emily and NSERC for a fantasRc experience NASA ocials for supporRng the program Steve Barbosa and Aaron Katzenstein at AQMD P-3 ight crew

QuesRons?