Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 5 2008 10.5194/acp-8-1139-2008 http://www.atmos-chem-phys.net/8/1139/2008/ http://www.atmos-chem-phys.net/8/1139/2008/acp-8-1139-2008.html http://www.atmos-chem-phys.net/8/1139/2008/acp-8-1139-2008.pdf 1139 1152 2008-02-28 Evolving mass spectra of the oxidized component of organic aerosol: results from aerosol mass spectrometer analyses of aged diesel emissions A. M. Sage E. A. Weitkamp A. L. Robinson N. M. Donahue nmd@cmu.edu Center for Atmospheric Particle Studies, Carnegie Mellon University; Pittsburgh, PA 15213, USA The species and chemistry responsible for secondary organic aerosol (SOA) formation remain highly uncertain. Laboratory studies of the oxidation of individual, high-flux SOA precursors do not lead to particles with mass spectra (MS) matching those of ambient aged organic material. Additionally, the complexity of real organic particles challenges efforts to identify their chemical origins. We have previously hypothesized that SOA can form from the atmospheric oxidation of a large suite of precursors with varying vapor pressures. Here, we support this hypothesis by using an aerosol mass spectrometer to track the chemical evolution of diesel exhaust as it is photochemically oxidized in an environmental chamber. With explicit knowledge of the condensed-phase MS of the primary emissions from our engine, we are able to decompose each recorded MS into contributing primary and secondary spectra throughout the experiment. We find that the SOA becomes increasingly oxidized as a function of time, quickly approaching a final MS that closely resembles that of ambient aged organic particulate matter. This observation is consistent with our hypothesis of an evolving suite of SOA precursors. Low vapor pressure, semi-volatile organic emissions can form condensable products with even a single generation of oxidation, resulting in an early-arising, relatively less-oxidized SOA. Continued gas-phase oxidation can form highly oxidized SOA in surprisingly young air masses via reaction mechanisms that can add multiple oxygen atoms per generation and result in products with sustained or increased reactivity toward OH. 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., Zhang, Q., Sun, Y., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Alfarra, R., Prevot, A. S. H., Dommen, J., Duplissy, J., Metzer, 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., in press, 2008. Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A A., Dommen, J., Prévôt, A. S. H., Worsnopf, D R., Baltensperger, U., and Coe, H.: A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber, Atmos. Chem. Phys., 6, 5279–5293, 2006. Alfarra, M R., Coe, H., Allan, J D., Bower, K N., Boudries, H., Canagaratna, M R., Jimenez, J L., Jayne, J T., Garforth, A A., Li, S M., and Worsnop, D R.: Characterization of urban and rural organic particulate in the lower Fraser valley using two aerodyne aerosol mass spectrometers, Atmos. Environ., 38, 5745–5758, 2004. Allan, J D., Coe, H., Bower, K., Alfarra, M R., Delia, A., Jimenez, J L., Middlebrook, A., Drewnick, F., Onasch, T B., Canagaratna, M R., Jayne, J T., and Worsnop, D R.: Technical note: Extraction of chemically resolved mass spectra from Aerodyne Aerosol mass spectrometer data, J. Aerosol Sci., 35, 922, 2004a. 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 Worsnopf, 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, 2004b. Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003. Bahreini, R., Keywood, M D., Ng, N L., Varutbangkul, V., Gao, S., Flagan, R., Seinfeld, J., Worsnop, D R., and Jimenez, J L.: Measurements of Secondary Organic Aerosol (SOA) from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne Aerosol Mass Spectrometer, Environ. Sci. Technol., 39, 5674–5688, doi:10.1021/es048061a, 2005. Baltensperger, U., Kalberer, M., Dommen, J., Paulsen, D., Alfarra, M., Coe, H., Fisseha, R., Gascho, A., Gysel, M., Nyeki, S., Sax, M., Steinbacher, M., A.S.H., P., Sjogren, S., Weingartner, E., and Zenobi, R.: Secondary Organic aerosols from antrhopogenic and biogenic precursors, Faraday Discuss., 130, 265–278, doi:10.1039/b417367h, 2005. Canagaratna, M R., Jayne, J T., Ghertner, D A., Herndon, S., Shi, Q., Jimenez, J L., Silva, P J., Williams, P., Lanni, T., Drewnick, F., Demerjian, K L., Kolb, C E., and Worsnop, D R.: Chase studies of particulate emissions from in-use New York City vehicles, Aerosol Sci. Tech., 38, 555–573, 2004. Chattopadhyay, S., Tobias, H J., and Ziemann, P J.: A method for measuring vapor pressures of low-volatility organic aerosol compounds using a thermal desorption particle beam mass spectrometer, Anal. Chem., 73, 3797–3803, 2001. de~Gouw, J A., Middlebrook, A M., Warneke, C., Goldan, P D., Kuster, W C., Roberts, J M., Fehsenfeld, F C., Worsnop, D R., Canagaratna, M R., Pszenny, A. A P., Keene, W C., Marchewka, M., Bertman, S B., and Bates, T S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res., 110, D16 305, doi:10.1029/2004JD005623, 2005. Goldstein, A. and Galbally, I.: Known and Unexplored Organic Constituents in the Earth's Atmosphere, Environ. Sci. Technol., 41, 1515–1520, 2007. Hamilton, J., Webb, P., Lewis, A., Hopkins, J., Smith, S., and Davy, P.: Partially Oxidised Organic Components in Urban Aerosol Using GC x GC-TOF/MS, Atmos. Chem. Phys., 4, 1279–1290, 2004. Heald, C., Jacob, D., Park, R., Russell, L., Huebert, B., Seinfeld, J., Liao, H., and Weber, R.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18 809, doi:10.1029/2005GL023831, 2005. Huff~Hartz, K E., Rosenørn, T., Ferchak, S R., Raymond, T M., Bilde, M., Donahue, N M., and Pandis, S N.: Cloud Condensation Nuclei Activation of Monoterpene and Sesquiterpene Secondary Organic Aerosol, J. Geophys. Res., 110, D14 208, http://www.agu.org/pubs/crossref/2005.../2004JD005754.shtml, 2005. Jayne, J T., Leard, D C., Zhang, X., 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., W., M J., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, J. Geophys. Res. Atmos., 108, 8425, 2003. Johnson, D., Utembe, S., Jenkin, M., Derwent, R., Hayman, G., Alfarra, M., Coe, H., and McFiggans, G.: Simulating regional scale secondary organic aerosol formation during the TORCH 2003 campaign in the southern UK, Atmos. Chem. Phys., 6, 403–418, 2006. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S H., Fisseha, R., Weingartner, E., Frankevic, V., Zenobi, R., and Baltensperger, U.: Identification of Polymers as Major Components of Atmospheric Organic Aerosols, Science, 303, 1659–1662, 2004. 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. Kondo, Y., Miyazaki, Y., Takegawa, N., Miyakawa, T., Weber, R., Jimenez, J L., Zhang, Q., and Worsnop, D R.: Oxygenated and water-soluble organic aerosols in Tokyo, J. Geophys. Res. Atmos., 112, D01 203, doi:10.1029/2006JD007056, 2007. Lanz, V., Alfarra, M., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503–1522, 2007. Lim, Y B. and Ziemann, P J.: Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx, Environ. Sci. Technol., 39, 9229–9236, 2005. Marcolli, C., Canagaratna, M R., Worsnop, D R., Bahreini, R., de~Gouw, J A., Warneke, C., Goldan, P D., Kuster, W C., Williams, E J., Lerner, B M., Roberts, J M., Meagher, J F., Fehsenfeld, F C., Marchewka, M., Bertman, S B., and Middlebrook, A M.: Cluster analysis of the organic peaks in bulk mass spectra obtained during the 2002 New England air quality study with an Aerodyne aerosol mass spectrometer, Atmos. Chem. Phys., 6, 5649–5666, 2006. Presto, A A., Huff~Hartz, K E., and Donahue, N M.: Secondary Organic Aerosol production from terpene ozonolysis: 1. Effect of UV radiation, Environ. Sci. Technol., 39, 7036–7045, http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/es050174m, 2005. Robinson, A L., Donahue, N M., and Rogge, W F.: Photochemical Oxidation and Changes in Molecular Composition of Organic Aerosol in the Regional Context, J. Geophys. Res., 111, D03 302, http://www.agu.org/pubs/crossref/2006.../2005JD006265.shtml, doi:10.1029/2005JD006265, 2006. Robinson, A L., Donahue, N M., Shrivastava, M. K., Weitkamp, E A., Sage, A M., Greishop, A. P., Lane, T E., Pierce, J. R., and Pandis, S N.: Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging, Science, 315, 1259–1262, 2007. Rogge, W F., Hildemann, L M., Mazurek, M A., Cass, G R., and Simoneit, B. R T.: Sources of Fine Organic Aerosol. 2. Noncatalyst and Catalyst-Equipped Automobiles and Heavy-Duty Diesel Trucks, Environ. Sci. Technol., 27, 636–651, 1993. Rudich, Y., Donahue, N M., and Mentel, T F.: Aging of organic aerosol: bridging the gap between laboratory and field studies, Annu. Rev. Phys. Chem., 58, 321–352, http://arjournals.annualreviews.org/doi/abs/10.1146/annurev.physchem.58.032806.104432, 2007. Salcedo, D., Onasch, T B., Dzepina, K., Canagaratna, M R., Zhang, Q., Huffman, J A., DeCarlo, P F., Jayne, J T., W., M J., 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. 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, 1578–1587, 1999. 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, L17 811, 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, 2007. Williams, B J., Goldstein, A H., Kreisberg, N M., and Hering, S V.: An in-situ instrument for speciated organic composition of atmospheric aerosols: Thermal Desorption Aerosol GC/MS-FID (TAG), Aerosol Sci. Tech., 40, 627–638, 2006. Zhang, J., Huff~Hartz, K. E., 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, 11 053–11 063, 2006. Zhang, Q.: Open source CPCA code, http://www.asrc.cestm.albany.edu/qz/, 2005. Zhang, Q., Alfarra, M R., Worsnop, D R., Allan, J., Coe, H., Canagaratna, M R., and Jimenez, J L.: Deconvolution and Quantification of Hydrocarbon-like and Oxygenated Organic Aerosols Based on Aerosol Mass Spectrometry, Environ. Sci. Technol., 39, 4938–4952, 2005a. Zhang, Q., Worsnop, D R., Canagaratna, M R., and Jimenez, J L.: Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols., Atmos. Chem. Phys., 5, 3289–3311, 2005b. Zhang, Q., Jimenez, J L., Canagaratna, M R., Allan, J D., Coe, H., Ulbrick, I., Alfarra, M., Takami, A., Middlebrook, A., Sun, Y., K., D., Dunlea, E., Docherty, K., DeCarlo, P F., Salcedo, D., Onasch, T B., Jayne, J T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Weimer, S., Demerjian, K., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R., Rautiainen, J., Sun, J., Zhang, Y., and Worsnop, D R.: Ubiquity and Dominance of Oxygenated Species in Organic Aerosols in Anthropogenically-Influenced Northern Hemisphere Mid-latitudes, Geophys. Res. Lett., 34, L13 801, doi:10.1029/2007GL029979, 2007.