Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 9 2009 10.5194/acp-9-2973-2009 http://www.atmos-chem-phys.net/9/2973/2009/ http://www.atmos-chem-phys.net/9/2973/2009/acp-9-2973-2009.html http://www.atmos-chem-phys.net/9/2973/2009/acp-9-2973-2009.pdf 2973 2986 2009-05-07 High formation of secondary organic aerosol from the photo-oxidation of toluene L. Hildebrandt N. M. Donahue S. N. Pandis Center for Atmospheric Particle Studies, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, PA 15213, USA Institute of Chemical Engineering and High Temperature Chemical Processes (ICE-HT), Foundation of Research and Technology (FORTH), Patra, Greece Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA) precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NO_x conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NO_x conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available. Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A. M., Northway, M. J., Ziemann, P. J., Canagaratna, M. R., Alfarra, M. R., Prevot, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high resolution time-of-flight aerosol mass spectrometry, Environ. Sci. Technol., 42, 4478–4485, 2008. Allan, J. D., Delia, A. E., Coe, H., Bower, K. N., Alfarra, M. R., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnop, D. R.: A generalised method for the extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, 2004. An, W. J., Pathak, R. K., Lee, B.-H., and Pandis, S. N.: Aerosol volatility measurement using an improved thermodenuder: Application to secondary organic aerosol, J. Aerosol Sci., 38, 305–314, 2007. Carter, W. P. L., Cocker, D. R., Fitz, D. R., Malkina, I. L., Bumiller, K., Sauer, C. G., Pisano, J. T., Bufalino, C., and Song, C.: A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation, Atmos. Environ., 39, 7768–7788, 2005. Crump, J. G. and Seinfeld, J. H.: Turbulent Deposition and Gravitational Sedimentation of an Aerosol in a Vessel of Arbitrary Shape, J. Aerosol Sci., 12, 405–415, 1981. Davidson, C. I., Phalen, R. F., and Solomon, P. A.: Airborne particulate matter and human health: A review, Aerosol Sci. Tech., 39, 737–749, 2005. de Gouw, J. A., Goldan, P. D., Warneke, C., Kuster, W. C., Roberts, J. M., Marchewka, M., Bertman, S. B., Pszenny, A. A. P., and Keene, W. C.: Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002, J. Geophys. Res.- Atmos., 108, 4682, doi:10.1029/2003jd003863, 2003. Dockery, D. W., Pope, C. A., Xu, X. P., Spengler, J. D., Ware, J. H., Fay, M. E., Ferris, B. G., and Speizer, F. E.: An association between air-pollution and mortality in 6 United-States cities, New Engl. J. Med., 329, 1753–1759, 1993. Donahue, N. M., Robinson, A. L., Stanier, C. O., and Pandis, S. N.: Coupled partitioning, dilution, and chemical aging of semivolatile organics, Environ. Sci. Technol., 40, 2635–2643, 2006. Edney, E. O., Driscoll, D. J., Speer, R. E., Weathers, W. S., Kleindienst, T. E., Li, W., and Smith, D. F.: Impact of aerosol liquid water on secondary organic aerosol yields of irradiated toluene/propylene/NO_x/(NH$_4)_2$SO₄/air mixtures, Atmos. Environ., 34, 3907–3919, 2000. Forstner, H. J. L.: Aerosol Formation from Atmospheric Hydrocarbon Photooxidation, Doctor of Philosophy, Chemical Engineering, California Institute of Technology, Pasadena, USA, 381~pp., 1996. Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the Earth's atmosphere, Environ. Sci. Technol., 41, 1515–1521, 2007. Grieshop, A. P., Donahue, N. M., and Robinson, A. L.: Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?, Geophys. Res. Lett., 34, L14810, doi:10.1029/2007gl029987, 2007. Hennigan, C. J., Bergin, M. H., Dibb, J. E., and Weber, R. J.: Enhanced secondary organic aerosol formation due to water uptake by fine particles, Geophys. Res. Lett., 35, L18801, doi:10.1029/2008gl035046, 2008. Hurley, M. D., Sokolov, O., Wallington, T. J., Takekawa, H., Karasawa, M., Klotz, B., Barnes, I., and Becker, K. H.: Organic aerosol formation during the atmospheric degradation of toluene, Environ. Sci. Technol., 35, 1358–1366, 2001. IPCC: Climate Change 2007 – The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the IPCC, 2007. Izumi, K. and Fukuyama, T.: Photochemical aerosol formation from aromatic-hydrocarbons in the presence of NO_x, Atmos. Environ. A-Gen., 24, 1433–1441, 1990. Jayne, J. T., Leard, D. C., Zhang, X. F., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. R.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Tech., 33, 49–70, 2000. Jimenez, J. L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, J. Geophys. Res.- Atmos., 108, 8425–8437, 2003. Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005. Karydis, V. A., Tsimpidi, A. P., and Pandis, S. N.: Evaluation of a three-dimensional chemical transport model (PMCAMx) in the eastern United States for all four seasons, J. Geophys. Res.-Atmos., 112, D14211, doi:10.1029/2006jd007890, 2007. Kleindienst, T. E., Smith, D. F., Li, W., Edney, E. O., Driscoll, D. J., Speer, R. E., and Weathers, W. S.: Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol, Atmos. Environ., 33, 3669–3681, 1999. Kleindienst, T. E., Conver, T. S., McIver, C. D., and Edney, E. O.: Determination of secondary organic aerosol products from the photooxidation of toluene and their implications in ambient PM$_2.5$, J. Atmos. Chem., 47, 79–100, 2004. Koo, B. Y., Ansari, A. S., and Pandis, S. N.: Integrated approaches to modeling the organic and inorganic atmospheric aerosol components, Atmos. Environ., 37, 4757–4768, 2003. Kroll, J. H., Chan, A. W. H., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Reactions of semivolatile organics and their effects on secondary organic aerosol formation, Environ. Sci. Technol., 41, 3545–3550, 2007. LADCO – The Lake Michigan Air Directors Consortium: Midwest Regional Planning Organization: Base~E Modeling Inventory, online available at: www.ladco.org, 1999. Lane, T. E., Donahue, N. M., and Pandis, S. N.: Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model, Atmos. Environ., 42, 7439–7451, doi:10.1016/j.atmosenv.2008.06.026, 2008. McMurry, P. H. and Rader, D. J.: Aerosol wall losses in electrically charged chambers, Aerosol Sci. Tech., 4, 249–268, 1985. Ng, N. L., Kroll, J. H., Chan, A. W. H., Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from m-xylene, toluene, and benzene, Atmos. Chem. Phys., 7, 3909–3922, 2007. Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, 1996. Pandis, S. N., Harley, R. A., Cass, G. R., and Seinfeld, J. H.: Secondary organic aerosol formation and transport, Atmos. Environ. A-Gen., 26, 2269–2282, 1992. Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of alpha-pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields), J. Geophys. Res.-Atmos., 112, D03201, doi:10.1029/2006jd007436, 2007. Pierce, J. R., Engelhart, G. J., Hildebrandt, L., Weitkamp, E. A., Pathak, R. K., Donahue, N. M., Robinson, A. L., Adams, P. J., and Pandis, S. N.: Constraining particle evolution from wall losses, coagulation, and condensation-evaporation in smog-chamber experiments: Optimal estimation based on size distribution measurements, Aerosol Sci. Tech., 42, 100–1015, doi:10.1080/02786820802389251, 2008. Presto, A. A. and Donahue, N. M.: Investigation of a-pinene + ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006. Sage, A. M., Weitkamp, E. A., Robinson, A. L., and Donahue, N. M.: Evolving mass spectra of the oxidized component of organic aerosol: results from aerosol mass spectrometer analyses of aged diesel emissions, Atmos. Chem. Phys., 8, 1139–1152, 2008. Song, C., Na, K., Warren, B., Malloy, Q., and Cocker, D. R.: Impact of propene on secondary organic aerosol formation from m-xylene, Environ. Sci. Technol., 41, 6990–6995, 2007. Stanier, C. O., Donahue, N., and Pandis, S. N.: Parameterization of secondary organic aerosol mass fractions from smog chamber data, Atmos. Environ., 42, 2276–2299, doi:10.1016/j.atmosenv.2007.12.042, 2008. Stern, J. E.: Aerosol Formation and Growth in Aromatic Hydrocarbon/NO$_\rm x$ Systems, Doctor of Philosophy, Chemical Engineering, California Institute of Technology, Pasadena, USA, 632~pp., 1988. Takekawa, H., Minoura, H., and Yamazaki, S.: Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons, Atmos. Environ., 37, 3413–3424, 2003. Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected, Geophys. Res. Lett., 33, L17811, doi:10.1029/2006gl026899, 2006. Volkamer, R., Ziemann, P. J., and Molina, M. J.: Secondary Organic Aerosol Formation from Acetylene (C₂H₂): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase, Atmos. Chem. Phys., 9, 1907–1928, 2009. Vutukuru, S., Griffin, R. J., and Dabdub, D.: Simulation and analysis of secondary organic aerosol dynamics in the South Coast Air Basin of California, J. Geophys. Res.-Atmos., 111, D10S12, doi:10.1029/2005jd006139, 2006. Weitkamp, E. A., Sage, A. M., Pierce, J. R., Donahue, N. M., and Robinson, A. L.: Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber, Environ. Sci. Technol., 41, 6969–6975, doi:10.1021/es070193r, 2007. Zhang, J. Y., Hartz, K. E. H., Pandis, S. N., and Donahue, N. M.: Secondary organic aerosol formation from limonene ozonolysis: Homogeneous and heterogeneous influences as a function of NO_x, J. Phys. Chem. A, 110, 11053–11063, 2006. Zhang, Q., Jimenez, J. L., Canagaratna, M. R., Allan, J. D., Coe, H., Ulbrich, I., Alfarra, M. R., Takami, A., Middlebrook, A. M., Sun, Y. L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P. F., Salcedo, D., Onasch, T., Jayne, J. T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R. J., Rautiainen, J., Sun, J. Y., Zhang, Y. M., and Worsnop, D. R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13801, doi:10.1029/2007gl029979, 2007.