Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 5 2008 10.5194/acp-8-1249-2008 http://www.atmos-chem-phys.net/8/1249/2008/ http://www.atmos-chem-phys.net/8/1249/2008/acp-8-1249-2008.html http://www.atmos-chem-phys.net/8/1249/2008/acp-8-1249-2008.pdf 1249 1259 2008-03-04 Source apportionment of fine organic aerosol in Mexico City during the MILAGRO experiment 2006 E. A. Stone D. C. Snyder R. J. Sheesley A. P. Sullivan R. J. Weber J. J. Schauer jjschauer@wisc.edu Environmental Chemistry and Technology, University of Wisconsin-Madison, Madison, WI, USA, 53706 School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA, 30332 Organic carbon (OC) comprises a large fraction of fine particulate matter (PM_2.5) in Mexico City. Daily and select 12-h PM_2.5 samples were collected in urban and peripheral sites in Mexico City from 17–30 March 2006. Samples were analyzed for OC and elemental carbon (EC) using thermal-optical filter-based methods. Real-time water-soluble organic carbon (WSOC) was collected at the peripheral site. Organic compounds, particularly molecular markers, were quantified by soxhlet extraction with methanol and dichloromethane, derivitization, and gas chromatography with mass spectrometric detection (GCMS). A chemical mass balance model (CMB) based on molecular marker species was used to determine the relative contribution of major sources to ambient OC. Motor vehicles, including diesel and gasoline, consistently accounted for 49% of OC in the urban area and 32% on the periphery. The daily contribution of biomass burning to OC was highly variable, and ranged from 5–26% at the urban site and 7–39% at the peripheral site. The remaining OC unapportioned to primary sources showed a strong correlation with WSOC and was considered to be secondary in nature. Comparison of temporally resolved OC showed that contributions from primary aerosol sources during daylight hours were not significantly different from nighttime. This study provides quantitative understanding of the important sources of OC during the MILAGRO 2006 field campaign. Bae, M. S., Schauer, J. J., DeMinter, J. T., and Turner, J. R.: Hourly and daily patterns of particle-phase organic and elemental carbon concentrations in the urban atmosphere, J. Air Waste Manage., 54(7), 823–833, 2004. Cahill, T. M., Seaman, V. Y., Charles, M. J., Holzinger, R., and Goldstein, A. H.: Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California, J. Geophys. Res.-Atmos., 111(D16), D16312, doi:10.1029/2006JD007178, 2006. Caplan, K. J.: Rotameter Corrections For Gas-Density, Am. Ind. Hyg. Assoc. J., 46(11), B10–16, 1985. Chow, J. C., Watson, J. G., Edgerton, S. A., Vega, E., and Ortiz, E.: Spatial differences in outdoor PM10 mass and aerosol composition in Mexico City, J. Air Waste Manage., 52(4), 423–434, 2002. Dockery, D. W., Schwartz, J., and Spengler, J. D.: Air-Pollution And Daily Mortality – Associations With Particulates And Acid Aerosols, Environ. Res., 59(2), 362–373, 1992. Edgerton, S. A., Bian, X., Doran, J. C., Fast, J. D., Hubbe, J. M., Malone, E. L., Shaw, W. J., Whiteman, C. D., Zhong, S., Arriaga, J. L., Ortiz, E., Ruiz, M., Sosa, G., Vega, E., Limon, T., Guzman, F., Archuleta, J., Bossert, J. E., Elliot, S. M., Lee, J. T., McNair, L. A., Chow, J. C., Watson, J. G., Coulter, R. L., Doskey, P. V., Gaffney, J. S., Marley, N. A., Neff, W., and Petty, R.: Particulate air pollution in Mexico City: A collaborative research project, J. Air Waste Manage., 49(10), 1221–1229, 1999. Fast, J. D., De Foy, B., Acevedo Rosas, F., Caetano, E., Carmichael, G., Emmons, L., McKenna, D., Mena, M., Skamarock, W., Tie, X., Coulter, R. L., Barnard, J. C., Wiedinmyer, C.,and Madronich, S.: A meteorological overview of the MILAGRO field campaigns, Atmos. Chem. Phys., 7, 2233–2257, 2007. Feng, J. L., Hu, M., Chan, C. K., Lau, P. S., Fang, M., He, L. Y., and Tang, X. Y.: A comparative study of the organic matter in PM2.5 from three Chinese megacities in three different climatic zones, Atmos. Environ., 40(21), 3983–3994, 2006. Fine, P. M., Chakrabarti, B., Krudysz, M., Schauer, J. J., and Sioutas, C.: Diurnal variations of individual organic compound constituents of ultrafine and accumulation mode particulate matter in the Los Angeles basin, Environ. Sci. Technol., 38(5), 1296–1304, 2004. Fraser, M. P. and Lakshmanan, K.: Using levoglucosan as a molecular marker for the long-range transport of biomass combustion aerosols, Environ. Sci. Technol., 34(21), 4560–4564, 2000. Johnson, K. S., de Foy, B., Zuberi, B., Molina, L. T., Molina, M. J., Xie, Y., Laskin, A.,and Shutthanandan, V.: Aerosol composition and source apportionment in the Mexico City Metropolitan Area with PIXE/PESA/STIM and multivariate analysis, Atmos. Chem. Phys., 6, 4591–4600, 2006. Lough, G. C., Christenson, C. C., Schauer, J. J., Tortorelli, J., Bean, E., Lawson, D., Clark, N. N., and Gabele, P. A.: Development of Molecular Marker Source Profiles for Emissions from On-Road Gasoline and Diesel Vehicle Fleets, J. Air Waste Manage., 57(10), 1190–1199, 2007. Marr, L. C., Dzepina, K., Jimenez, J. L., Reisen, F., Bethel, H. L., Arey, J., Gaffney, J. S., Marley, N. A., Molina, L. T., and Molina, M. J.,: Sources and transformations of particle-bound polycyclic aromatic hydrocarbons in Mexico City, Atmos. Chem. Phys., 6, 1733–1745, 2006. Molina, L. T. and Molina, M. J.: Improving air quality in megacities – Mexico City Case Study, Ann. NY. Acad. Sci., p 1023, 142–158, 2004. National Center for Atmospheric Research, Earth Observing Laboratory (NCAR/EOL): MILAGRO, available at: www.eol.ucar.edu/projects/milagro, last access: October 2007, 2006. Nolte, C. G., Schauer, J. J., Cass, G. R., and Simoneit, B. R. T.: Trimethylsilyl derivatives of organic compounds in source samples and in atmospheric fine particulate matter, Environ. Sci. Technol., 36(20), 4273–4281, 2002. Oros, D. R. and Simoneit, B. R. T.: Identification and emission rates of molecular tracers in coal smoke particulate matter, Fuel, 79(5), 515–536, 2000. Raga, G. B., Baumgardner, D., Castro, T., Martinez-Arroyo, A., and Navarro-Gonzalez, R.: Mexico City air quality: a qualitative review of gas and aerosol measurements (1960–2000), Atmos. Environ., 35(23), 4041–4058, 2001. Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simoneit, B. R. T.: Sources Of Fine Organic Aerosol, 4. Particulate Abrasion Products From Leaf Surfaces Of Urban Plants, Environ. Sci. Technol., 27(13), 2700–2711, 1993a. Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simoneit, B. R. T.: Sources Of Fine Organic Aerosol, 5. Natural-Gas Home Appliances, Environ. Sci. Technol., 27(13), 2736–2744, 1993b. Salcedo, D., Onasch, T. B., Dzepina, K., Canagaratna, M. R., Zhang, Q., Huffman, J. A., DeCarlo, P. F., Jayne, J. T., Mortimer, P., Worsnop, D. R., Kolb, C. E., Johnson, K. S., Zuberi, B., Marr, L. C., Volkamer, R., Molina, L. T., Molina, M. J., Cardenas, B., Bernabe, R. M., Marquez, C., Gaffney, J. S., Marley, N. A., Laskin, A., Shutthanandan, V., Xie, Y., Brune, W., Lesher, R., Shirley, T., and Jimenez, J. L.: Characterization of ambient aerosols in Mexico City during the MCMA-2003 campaign with Aerosol Mass Spectrometry: results from the CENICA Supersite, Atmos. Chem. Phys., 6, 925–946, 2006. Saldiva, P. H. N., Pope, C. A., Schwartz, J., Dockery, D. W., Lichtenfels, A. J., Salge, J. M., Barone, I., and Bohm, G. M.: Air-Pollution And Mortality In Elderly People – A Time-Series Study In Sao-Paulo, Brazil, Arch. Environ. Health., 50(2), 159–163, 1995. Sannigrahi, P., Sullivan, A. P., Weber, R. J., and Ingall, E. D.: Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state C-13 NMR spectroscopy, Environ. Sci. Technol., 40(3), 666–672, 2006. Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources, 2. C-1 through C-30 organic compounds from medium duty diesel trucks, Environ. Sci. Technol., 33(10), 1578–1587, 1999. Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources, 5. C-1-C-32 organic compounds from gasoline-powered motor vehicles, Environ. Sci. Technol., 36(6), 1169–1180, 2002. Schauer, J. J., Mader, B. T., Deminter, J. T., Heidemann, G., Bae, M. S., Seinfeld, J. H., Flagan, R. C., Cary, R. A., Smith, D., Huebert, B. J., Bertram, T., Howell, S., Kline, J.T., Quinn, P., Bates, T., Turpin, B., Lim, H. J., Yu, J. Z., Yang, H., and Keywood, M. D.: ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon, Environ. Sci. Technol., 37(5), 993–1001, 2003. Schauer, J. J., Rogge, W. F., Hildemann, L. M., Mazurek, M. A., and Cass, G. R.: Source apportionment of airborne particulate matter using organic compounds as tracers, Atmos. Environ., 30(22), 3837–3855, 1996. Schifter, I., Diaz, L., Avalos, S., Vera, N., Mejia, I., Reyes, F., and Lopez-Salinas, E.: Trends of exhaust emissions from gasoline motor vehicles in the metropolitan area of Mexico city, Int. J. Environ. Pollut., 21(2), 166–174, 2004. Schwartz, J. and Marcus, A.: Mortality And Air-Pollution In London – A Time-Series Analysis, Am. J. Epidemiol., 131(1), 185–194, 1990. Sheesley, R. J., Schauer, J. J., Bean, E., and Kenski, D.: Trends in secondary organic aerosol at a remote site in Michigan's upper peninsula, Environ. Sci. Technol., 38(24), 6491–6500, 2004. Sheesley, R. J., Schauer, J. J., Zheng, M., and Wang, B.: Sensitivity of molecular marker-based CMB models to biomass burning source profiles, Atmos. Environ., 41, 9050–9063, 2007. Simoneit, B. R. T.,: A review of biomarker compounds as source indicators and tracers for air pollution, Environ. Sci. Pollut. R., 6(3), 159–169, 1999. Simoneit, B. R. T.: Biomass burning – A review of organic tracers for smoke from incomplete combustion, Appl. Geochem., 17(3), 129–162, 2002. Simoneit, B. R. T., Schauer, J. J., Nolte, C. G., Oros, D. R., Elias, V. O., Fraser, M. P., Rogge, W. F., and Cass, G. R.: Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles, Atmos. Environ., 33(2), 173–182, 1999. Sullivan, A. P., Weber, R. J., Clements, A. L., Turner, J. R., Bae, M. S., and Schauer, J. J.: A method for on-line measurement of water-soluble organic carbon in ambient aerosol particles: Results from an urban site, Geophys. Res. Lett., 31(13), L13105, doi:10.1029/2004GL019681, 2004. Sun, J. M. and Ariya, P. A.: Atmospheric organic and bio-aerosols as cloud condensation nuclei (CCN): A review, Atmos. Environ., 40(5), 795–820, 2006. 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. Yokelson, R., Urbanski, S., Atlas, E., Toohey, D., Alvarado, E., Crounse, J., Wennberg, P., Fisher, M., Wold, C., Campos, T., Adachi, K., Busek, P. R., and Hao, W. M.: Emissions from forest fires near Mexico City, Atmos. Chem. Phys. Discuss., 7, 6687–6718, 2007. Yu, J. Z., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 34(2), 207–258, 1999.