ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-5669-2009 Modeling of secondary organic aerosol yields from laboratory chamber data Chan M. N. 1 Chan A. W. H. 2 Chhabra P. S. 2 Surratt J. D. 2 Seinfeld J. H. 1 2 Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA 10 08 2009 9 15 5669 5680 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/9/5669/2009/acp-9-5669-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/5669/2009/acp-9-5669-2009.pdf

Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NO<sub>x</sub> conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice.

 References Aiken, A C., DeCarlo, P F., and Jimenez, J L.: Elemental analysis of organic species with electron ionization high-resolution mass spectrometry, Anal. Chem., 79, 8350–8358, 2007. Aiken, A C., Decarlo, P F., Kroll, J H., Worsnop, D R., Huffman, J A., Docherty, K S., Ulbrich, I M., Mohr, C., Kimmel, J R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A., Northway, M., Ziemann, P J., Canagaratna, M R., Onasch, T B., 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. Bahreini, R., Keywood, M D., Ng, N L., Varutbangkul, V., Gao, S., Flagan, R C., Seinfeld, J H., Worsnop, D R., and Jimenez, J L.: Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer, Environ. Sci. Technol., 39, 5674–5688, 2005. Bilde, M. and Pandis, S N.: Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene, Environ. Sci. Technol., 35, 3344–3349, 2001. Canagaratna, M R., Jayne, J T., Jimenez, J L., Allan, J D., Alfarra, M R., Zhang, Q., Onasch, T B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L R., Trimborn, A M., Northway, M J., DeCarlo, P F., Kolb, C E., Davidovits, P., and Worsnop, D R.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass. Spectrom. Rev., 26, 185–222, 2007. Chan, A. W. H., Kroll, J. H., Ng, N. L., and Seinfeld, J. H.: Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products, Atmos. Chem. Phys., 7, 4135–4147, 2007. Chen, J J. and Griffin, R J.: Modeling secondary organic aerosol formation from oxidation of alpha-pinene, beta-pinene, and d-limonene, Atmos. Environ., 39, 7731–7744, 2005. Claeys, M., Iinuma, Y., Szmigielski, R., Surratt, J D., Blockhuys, F., Van~Alsenoy, C., Böge, O., Sierau, B., Gómez-González, Y., Vermeylen, R., Van~der Veken, P., Shahgholi, M., Chan, A. W H., Herrmann, H., Seinfeld, J H., and Maenhaut, W.: Terpenylic acid and related compounds from the oxidation of α-pinene: Implications for new particle formation and growth above forests, Environ. Sci. Technol., in press, 2009. Cocker, D R., Flagan, R C., and Seinfeld, J H.: State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35, 2594–2601, 2001. DeCarlo, P F., Kimmel, J R., Trimborn, A., Northway, M J., Jayne, J T., Aiken, A C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K S., Worsnop, D R., and Jimenez, J L.: Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer, Anal. Chem., 78, 8281–8289, 2006. Docherty, K S., Wu, W., Lim, Y B., and Ziemann, P J.: Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O-3, Environ. Sci. Technol., 39, 4049–4059, 2005. 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. Dzepina, K., Volkamer, R. M., Madronich, S., Tulet, P., Ulbrich, I. M., Zhang, Q., Cappa, C. D., Ziemann, P. J., and Jimenez, J. L.: Evaluation of new secondary organic aerosol models for a case study in Mexico City, Atmos. Chem. Phys. Discuss., 9, 4417–4488, 2009. Gao, S., Keywood, M., Ng, N L., Surratt, J., Varutbangkul, V., Bahreini, R., Flagan, R C., and Seinfeld, J H.: Low-molecular-weight and oligomeric components in secondary organic aerosol from the ozonolysis of cycloalkenes and alpha-pinene, J. Phys. Chem. A, 108, 10147–10164, 2004. Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5235, 2009. Iinuma, Y., Boge, O., Gnauk, T., and Herrmann, H.: Aerosol-chamber study of the alpha-pinene/O-3 reaction: influence of particle acidity on aerosol yields and products, Atmos. Environ., 38, 761–773, 2004. Jenkin, M. E.: Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3, Atmos. Chem. Phys., 4, 1741–1757, 2004. Keywood, M D., Varutbangkul, V., Bahreini, R., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds, Environ. Sci. Technol., 38, 4157–4164, 2004. Kroll, J H. and Seinfeld, J H.: Representation of secondary organic aerosol laboratory chamber data for the interpretation of mechanisms of particle growth, Environ. Sci. Technol., 39, 4159–4165, 2005. Müller, L., Reinnig, M.-C., Warnke, J., and Hoffmann, Th.: Unambiguous identification of esters as oligomers in secondary organic aerosol formed from cyclohexene and cyclohexene/a-pinene ozonolysis, Atmos. Chem. Phys., 8, 1423–1433, 2008. Ng, N L., Kroll, J H., Keywood, M D., Bahreini, R., Varutbangkul, V., Flagan, R C., Seinfeld, J H., Lee, A., and Goldstein, A H.: Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 40, 2283–2297, 2006. 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. Pankow, J F.: An absorption-model of gas-particle partitioning of organic-compounds in the atmosphere, Atmos. Environ., 28, 185–188, 1994a. Pankow, J F.: An absorption-model of the gas aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994b. Pankow, J. F. and Asher, W. E.: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, 2008. Pankow, J F. and Chang, E I.: Variation in the sensitivity of predicted levels of atmospheric organic particulate matter (OPM), Environ. Sci. Technol., 42, 7321–7329, 2008. Pankow, J F., Seinfeld, J H., Asher, W E., and Erdakos, G B.: Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the alpha-pinene/, beta- pinene/, sabinene/, Delta(3)-carene/, and cyclohexene/ozone systems, Environ. Sci. Technol., 35, 1164–1172, 2001. 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. Presto, A A. and Donahue, N M.: Investigation of alpha-pinene plus ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006. Seinfeld, J H., Erdakos, G B., Asher, W E., and Pankow, J F.: Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, Delta(3)-Carene-, and cyclohexene-ozone systems, Environ. Sci. Technol., 35, 1806–1817, 2001. Shilling, J. E., Chen, Q., King, S. M., Rosenoern, T., Kroll, J. H., Worsnop, D. R., McKinney, K. A., and Martin, S. T.: Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of a-pinene, Atmos. Chem. Phys., 8, 2073–2088, 2008. Shilling, J. E., Chen, Q., King, S. M., Rosenoern, T., Kroll, J. H., Worsnop, D. R., DeCarlo, P. F., Aiken, A. C., Sueper, D., Jimenez, J. L., and Martin, S. T.: Loading-dependent elemental composition of α-pinene SOA particles, Atmos. Chem. Phys., 9, 771–782, 2009. 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, 2008. 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, 207–258, 1999.