References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-1741-2007

Evaluation of organic markers for chemical mass balance source apportionment at the Fresno Supersite

Chow

J. C.

¹ Watson

J. G.

¹ Lowenthal

D. H.

¹ Chen

L. W. A.

¹ Zielinska

¹ Mazzoleni

L. R.

² Magliano

K. L.

Desert Research Institute, Reno, NV, USA

Colorado State University, Fort Collins, CO, USA

California Air Resources Board, Sacramento, CA, USA

10 04 2007

7 7 1741 1754

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/7/1741/2007/acp-7-1741-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/1741/2007/acp-7-1741-2007.pdf

Sources of PM2.5 at the Fresno Supersite during high PM2.5 episodes occurring from 15 December 2000–3 February 2001 were estimated with the Chemical Mass Balance (CMB) receptor model. The ability of source profiles with organic markers to distinguish motor vehicle, residential wood combustion (RWC), and cooking emissions was evaluated with simulated data. Organics improved the distinction between gasoline and diesel vehicle emissions and allowed a more precise estimate of the cooking source contribution. Sensitivity tests using average ambient concentrations showed that the gasoline vehicle contribution was not resolved without organics. Organics were not required to estimate hardwood contributions. The most important RWC marker was the water-soluble potassium ion. The estimated cooking contribution did not depend on cholesterol because its concentrations were below the detection limit in most samples. Winter time source contributions were estimated by applying the CMB model to individual and average sample concentrations. RWC was the largest source, contributing 29–31% of measured PM2.5. Hardwood and softwood combustion accounted for 16–17% and 12–15%, respectively. Secondary ammonium nitrate and motor vehicle emissions accounted for 31–33% and 9–15%, respectively. The gasoline vehicle contribution (3–10%) was comparable to the diesel vehicle contribution (5–6%). The cooking contribution was 5–19% of PM2.5. Fresno source apportionment results were consistent with those estimated in previous studies.

References 1

Ashbaugh, L. L., Carvacho, O. F., Brown, M. S., Chow, J. C., Watson, J. G., and Magliano, K. L.: Soil sample collection and analysis for the Fugitive Dust Characterization Study, Atmos. Environ., 37(9–10), 1163–1173, 2003.

California Air Resources Board: Climate Change Emissions Inventory, Draft Report, prepared by California Environmental Protection Agency Air Resources Board, Sacramento, CA, 2004.

Chen, L.-W A., Chow, J. C., Watson, J G., Lowenthal, D H., and Chang, M.-C O.: Quantifying PM$_2.5$ source contributions for the San Joaquin Valley with multivariate receptor models, Environ. Sci. Technol., accepted, 2007.

Chow, J. C., Watson, J. G., Lowenthal, D. H., Solomon, P. A., Magliano, K. L., Ziman, S. D., and Richards, L. W.: PM$_10$ source apportionment in California's San Joaquin Valley, Atmos. Environ., 26A(18), 3335–3354, 1992.

Chow, J. C., Watson, J. G., Pritchett, L. C., Pierson, W. R., Frazier, C. A., and Purcell, R. G.: The DRI Thermal/Optical Reflectance carbon analysis system: Description, evaluation and applications in U.S. air quality studies, Atmos. Environ., 27A(8), 1185–1201, 1993.

Chow, J. C.: Critical review: Measurement methods to determine compliance with ambient air quality standards for suspended particles. J. Air Waste Manage. Assoc., 45, 320–382. 1995.

Chow, J. C., Watson, J. G., Lowenthal, D. H., and Countess, R. J.: Sources and chemistry of PM$_10$ aerosol in Santa Barbara County, CA, Atmos. Environ., 30(9), 1489–1499, 1996.

Chow, J. C. and Watson, J. G.: Ion chromatography in elemental analysis of airborne particles, in: Elemental Analysis of Airborne Particles, vol. 1, edited by: Landsberger, S. and Creatchman, M., Gordon and Breach Science, Amsterdam, 97–137, 1999.

Chow, J. C., Watson, J. G., Crow, D., Lowenthal, D. H., and Merrifield, T. M.: Comparison of IMPROVE and NIOSH carbon measurements, Aerosol Sci. Technol., 34(1), 23–34, 2001.

Chow, J. C. and Watson, J. G.: PM$_2.5$ carbonate concentrations at regionally representative Interagency Monitoring of Protected Visual Environment sites, J. Geophys. Res., 107(D21), ICC 6-1–ICC 6-9, 2002.

Chow, J. C., Watson, J. G., Ashbaugh, L. L., and Magliano, K. L.: Similarities and differences in PM$_10$ chemical source profiles for geological dust from the San Joaquin Valley, California, Atmos. Environ., 37(9–10), 1317–1340, 2003.

Chow, J. C., Watson, J. G., Chen, L.-W. A., Arnott, W. P., Moosmüller, H., and Fung, K. K.: Equivalence of elemental carbon by Thermal/Optical Reflectance and Transmittance with different temperature protocols, Environ. Sci. Technol., 38(16), 4414–4422, 2004a.

Chow, J. C., Watson, J. G., Kuhns, H. D., Etyemezian, V., Lowenthal, D. H., Crow, D. J., Kohl, S. D., Engelbrecht, J. P., and Green, M. C.: Source profiles for industrial, mobile, and area sources in the Big Bend Regional Aerosol Visibility and Observational (BRAVO) Study, Chemosphere, 54(2), 185–208, 2004b.

Chow, J. C., Chen, L.-W. A., Lowenthal, D. H., Doraiswamy, P., Park, K., Kohl, S., Trimble, D. L., and Watson, J. G.: California Regional PM$_10$/PM$_2.5$ Air Quality Study (CRPAQS) – Initial data analysis of field program measurements, prepared for California Air Resources Board, Sacramento, CA by Desert Research Institute, Reno, NV, 2005a.

Chow, J. C., Watson, J. G., Lowenthal, D. H., and Magliano, K. L.: Loss of PM$_2.5$ nitrate from filter samples in central California, J. Air Waste Manage. Assoc., 55(8), 1158–1168, 2005b.

Chow, J. C., Watson, J. G., Chen, L. W. A., Paredes-Miranda, G., Chang, M.-C. O., Trimble, D., Fung, K. K., Zhang, H., and Yu, J. Z.: Refining temperature measures in thermal/optical carbon analysis, Atmos. Chem. Phys., 5, 2961–2972, 2005c.

Chow, J. C., Chen, L.-W. A., Watson, J. G., Lowenthal, D. H., Magliano, K. L., Turkiewicz, K., and Lehrman, D.: PM$_2.5$ chemical composition and spatiotemporal variability during the California Regional PM$_10$/PM$_2.5$ Air Quality Study (CRPAQS), J. Geophys. Res., 111(D10), D10S04, doi:10.1029/2005JD006457, 2006a.

Chow, J. C., Watson, J. G., Lowenthal, D. H., Chen, L. W. A., and Magliano, K. L.: Particulate carbon measurements in California's San Joaquin Valley, Chemosphere, 62(3), 337–348, 2006b.

Dreyfus, M. A., Tolocka, M. P., Dodds, S. M., Dykins, J., and Johnston, M. V.: Cholesterol ozonolysis: Kinetics, mechanism and oligomer products, J. Phys. Chem. A, 109, 6242–6248, 2005.

Fitz, D. R., Chow, J. C., and Zielinska, B.: Development of a gas and particulate matter organic speciation profile database, prepared for Draft Final Report June 2003, Prepared fro San Joaquin Valleywide Air Pollution Study Agency; California Regional PM$_10$/PM$_2.5$ Air Quality Study by Desert Research Institute, Reno, NV, 2003.

Fraser, M. P., Cass, G. R., and Simoneit, B. R. T.: Air quality model evaluation data for organics 6. C3-C24 organic acids, Environ. Sci. Technol., 37(3), 446–453, 2003.

Fujita, E. M., Zielinska, B., Arnott, W. P., Campbell, D. E., Reinhart, L., Sagebiel, J. C., and Chow, J. C.: Gasoline/Diesel PM Split Study: Source and ambient sampling, chemical analysis, and apportionment phase, final report, prepared for National Renewable Energy Laboratory, Golden, CO by Desert Research Institute, Reno, NV, 2006.

Hannigan, M. P., Busby Jr., W. F., and Cass, G. R.: Source contributions to the mutagenicity of urban particulate air pollution, J. Air Waste Manage. Assoc., 55(4), 399–410, 2005.

Hidy, G. M. and Friedlander, S. K.: The nature of the Los Angeles aerosol, in: Proceedings of the Second International Clean Air Congress, edited by: Englund, H. M. and Beery, W. T., 391–404, 1971.

Hoffman, G. L. and Duce, R. A.: Copper contamination of atmospheric particulate samples collected with Gelman hurricane air sampler, Environ. Sci. Technol., 5, 1134–1136, 1971.

Javitz, H. S., Watson, J. G., and Robinson, N. F.: Performance of the chemical mass balance model with simulated local-scale aerosols, Atmos. Environ., 22, 10, 2309–2322, 1988.

Kim, B. M. and Henry, R. C.: Diagnostics for determining influential species in the chemical mass balance receptor model, J. Air Waste Manage. Assoc., 49(12), 1449–1455, 1999.

King, R. B. and Toma, J.: Copper emissions from a high-volume air sampler, NASA Technical Memorandum, 1975.

Labban, R., Veranth, J. M., Watson, J. G., and Chow, J. C.: Feasibility of soil dust source apportionment by pyrolysis-gas chromatography/mass spectrometry method, J. Air Waste Manage. Assoc., 56(9), 1230–1242. 2006.

Lowenthal, D. H., Chow, J. C., Watson, J. G., Neuroth, G. R., Robbins, R. B., Shafritz, B. P., and Countess, R. J.: The effects of collinearity on the ability to determine aerosol contributions from diesel- and gasoline-powered vehicles using the chemical mass balance model, Atmos. Environ., 26A(13), 2341–2351, 1992.

Magliano, K. L., Hughes, V. M., Chinkin, L. R., Coe, D. L., Haste, T. L., Kumar, N., and Lurmann, F. W.: Spatial and temporal variations in PM$_10$ and PM$_2.5$ source contributions and comparison to emissions during the 1995 Integrated Monitoring Study, Atmos. Environ., 33(29), 4757–4773, 1999.

Mamane, Y. and Gottlieb, J.: Nitrate formation on sea-salt and mineral particles - A single particle approach, Atmos. Environ., 26A(9), 1763–1769, 1992.

Manchester-Neesvig, J. B., Schauer, J. J., and Cass, G. R.: The distribution of particle-phase organic compounds in the atmosphere and their use for source apportionment during the Southern California Children's Health Study, J. Air Waste Manage. Assoc., 53(9), 1065–1079, 2003.

McDonald, J. D., Zielinska, B., Fujita, E. M., Sagebiel, J. C., Chow, J. C., and Watson, J. G.: Emissions from charbroiling and grilling of chicken and beef, J. Air Waste Manage. Assoc., 53(2), 185–194, 2003.

McDonald, J. D., Zielinska, B., Fujita, E. M., Sagebiel, J. C., Chow, J. C., and Watson, J. G.: Fine particle and gaseous emission rates from residential wood combustion, Environ. Sci. Technol., 34(11), 2080–2091, 2000.

Miguel, A. H., Kirchstetter, T. W., Harley, R. A., and Hering, S. V.: On-road emissions of particulate polycyclic aromatic hydrocarbons and black carbon soot from gasoline and diesel vehicles, Enivron. Sci. Technol., 32(4), 450–455, 1998.

Park, K., Chow, J. C., Watson, J. G., Trimble, D. L., Doraiswamy, P., Arnott, W. P., Stroud, K. R., Bowers, K., Bode, R., Petzold, A., and Hansen, A. D. A.: Comparison of continuous and filter-based carbon measurements at the Fresno Supersite, J. Air Waste Manage. Assoc., 56(4), 474–491, 2006.

Patterson, R. K.: Aerosol contamination from high volume sampler exhaust, J. Air Poll. Control Assoc., 30(2), 169–171, 1980.

Rinehart, L. R.: The origin of polar organic compounds in ambient fine particulate matter, Ph.D. Dissertation, University of Nevada, Reno, 2005.

Rinehart, L. R., Fujita, E. M., Chow, J. C., Magliano, K. L., and Zielinska, B.: Spatial distribution of PM$_2.5$ associated organic compounds in central California, Atmos. Environ., 40(2), 290–303, 2006.

Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simoneit, B. R. T.: Sources of fine organic aerosol – 1. Charbroilers and meat cooking operations, Enivron. Sci. Technol., 25(6), 1112–1125, 1991.

Schauer, J. J. and Cass, G. R.: Source apportionment of wintertime gas-phase and particle-phase air pollutants using organic compounds as tracers, Environ. Sci. Technol., 34(9), 1821–1832, 2000.

Schauer, J. J., Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Source apportionment of airborne particulate matter using organic compounds as tracers, Atmos. Environ., 30(22), 3837–3855, 1996.

Simoneit, B. R. T.: Organic matter of the troposphere – V: Application of molecular marker analysis to vehicular exhaust for source reconciliations, Int. J. Environ. Anal. Chem., 22, 203–233, 1985.

Turpin, B. J., Huntzicker, J. J., and Hering, S. V.: Investigation of organic aerosol sampling artifacts in the Los Angeles Basin, Atmos. Environ., 28, 19, 3061–3071, 1994.

U.S. EPA: SPECIATE database, http://www.epa.gov/ttn/chief/software/speciate/index.html, last accessed 13 February 2007.

Wang, D. and Hopke, P. K.: The use of constrained least-squares to solve the chemical mass balance problem, Atmos. Environ., 23(10), 2143–2150, 1989.

Watson, J. G., Cooper, J. A., and Huntzicker, J. J.: The effective variance weighting for least squares calculations applied to the mass balance receptor model, Atmos. Environ., 18(7), 1347–1355, 1984.

Watson, J. G., Chow, J. C., Lowenthal, D. H., Pritchett, L. C., Frazier, C. A., Neuroth, G. R., and Robbins, R.: Differences in the carbon composition of source profiles for diesel- and gasoline-powered vehicles, Atmos. Environ., 28(15), 2493–2505, 1994.

Watson, J. G., Robinson, N. F., Lewis, C. W., Coulter, C. T., Chow, J. C., Fujita, E. M., Lowenthal, D. H., Conner, T. L., Henry, R. C., and Willis, R. D.: Chemical mass balance receptor model version 8 (CMB) user's manual, prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC by Desert Research Institute, Reno, NV, 1997.

Watson, J. G., DuBois, D. W., DeMandel, R., Kaduwela, A. P., Magliano, K. L., McDade, C., Mueller, P. K., Ranzieri, A. J., Roth, P. M., and Tanrikulu, S.: Field program plan for the California Regional PM$_2.5$/PM$_10$ Air Quality Study (CRPAQS), prepared for California Air Resources Board, Sacramento, CA by Desert Research Institute, Reno, NV, 1998a.

Watson, J. G., Robinson, N. F., Lewis, C. W., Coulter, C. T., Chow, J. C., Fujita, E. M., Conner, T. L., and Pace, T. G.: CMB8 applications and validation protocol for PM$_2.5$ and VOCs, prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC by Desert Research Institute, Reno, NV, 1998b.

Watson, J. G., Chow, J. C., and Frazier, C. A.: X-ray fluorescence analysis of ambient air samples, in: Elemental Analysis of Airborne Particles, vol. 1, edited by: Landsberger, S. and Creatchman, M., Gordon and Breach Science, Amsterdam, 67–96, 1999.

Watson, J. G., Chow, J. C., Bowen, J. L., Lowenthal, D. H., Hering, S., Ouchida, P., and Oslund, W.: Air quality measurements from the Fresno Supersite, J. Air Waste Manage. Assoc., 50(8), 1321–1334, 2000.

Watson, J. G. and Chow, J. C.: A wintertime PM$_2.5$ episode at the Fresno, CA, supersite, Atmos. Environ., 36(3), 465–475, 2002.

Watson, J. G., Zhu, T., Chow, J. C., Engelbrecht, J. P., Fujita, E. M., and Wilson, W. E.: Receptor modeling application framework for particle source apportionment, Chemosphere, 49(9), 1093–1136, 2002a.

Watson, J. G., Chow, J. C., Lowenthal, D. H., Stolzenburg, M. R., Kreisberg, N. M., and Hering, S. V.: Particle size relationships at the Fresno supersite, J. Air Waste Manage. Assoc., 52(7), 822–827, 2002b.

Watson, J. G. and Chow, J. C.: Receptor models for air quality management, EM, 10, October, 27–36, 2004.

Watson, J. G. and Chow, J. C.: Receptor models, in: Air Quality Modeling – Theories, Methodologies, Computational Techniques, and Available Databases and Software, vol. II – Advanced Topics, edited by: Zannetti, P., Air Waste Manage. Assoc. and the EnviroComp Institute, Pittsburgh, PA, 455–501, 2005.

Watson, J. G., Chow, J. C., and Chen, L.-W. A.: Summary of organic and elemental carbon/black carbon analysis methods and intercomparisons, Aerosol Air Quality Res., 5(1), 65–102, 2005.

Watson, J. G., Chow, J. C., Lowenthal, D. H., Kreisberg, N., Hering, S. V., and Stolzenburg, M. R.: Variations of nanoparticle concentrations at the Fresno supersite, Sci. Total Environ., 358(1–3), 178–187, 2006a.

Watson, J. G., Chow, J. C., Park, K., and Lowenthal, D. H.: Nanoparticle and ultrafine particle events at the Fresno Supersite, J. Air Waste Manage. Assoc., 56(4), 417–430, 2006b.

Zheng, M., Cass, G. R., Schauer, J. J., and Edgerton, E. S.: Source apportionment of PM$_2.5$ in the southeastern United States using solvent-extractable organic compounds as tracers, Environ. Sci. Technol., 36(11), 2361–2371, 2002.

Zheng, M., Ke, L., Edgerton, E. S., Schauer, J. J., Dong, M. Y., and Russell, A. G.: Spatial distribution of carbonaceous aerosol in the southeastern United States using molecular markers and carbon isotope data, J. Geophys. Res., 111(D10), D10S06, doi:10.1029/2005JD006777, 2006.

Zielinska, B., McDonald, J. D., Hayes, T., Chow, J. C., Fujita, E. M., and Watson, J. G.: Northern Front Range Air Quality Study, Volume B: Source measurements, prepared for Colorado State University, Fort Collins, CO by Desert Research Institute, Reno, NV, 1998.

Zielinska, B. and Fujita, E. M.: Characterization of ambient volatile organic compounds at the western boundary of the SCOS97-NARSTO modeling domain, Atmos. Environ., 37, Suppl. 2, S171–S180, 2003.

Zielinska, B., Rinehart, L. R., and Goliff, W. S.: California Regional PM$_10$/PM$_2.5$ Air Quality Study – Organic compound measurements, prepared for California Air Resources Board, Sacramento, CA by Desert Research Institute, Reno, NV, 2003.

Zielinska, B., Sagebiel, J., Whitney, K., and Lawson, D. R.: Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles, J. Air Waste Manage. Assoc., 54(9), 1138–1150, 2004a.

Zielinska, B., Sagebiel, J., Arnott, W. P., Rogers, C. F., Kelly, K. E., Wagner, D. A., Lighty, J. S., Sarofim, A. F., and Palmer, G.: Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions, Environ. Sci. Technol., 38(9), 2557–2567, 2004b.