ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-3049-2009 Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs) Chan A. W. H. 1 Kautzman K. E. 1 Chhabra P. S. 1 Surratt J. D. 1 Chan M. N. 2 Crounse J. D. 1 Kürten A. 2 4 Wennberg P. O. 2 3 Flagan R. C. 1 2 Seinfeld J. H. 1 2 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, CA, USA Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA current affiliation: Institute for Atmospheric and Environmental Sciences, Goethe-University Frankfurt am Main, Frankfurt, Germany 12 05 2009 9 9 3049 3060 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/9/3049/2009/acp-9-3049-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/3049/2009/acp-9-3049-2009.pdf

Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m<sup>3</sup> chambers. Under high-NO<sub>x</sub> conditions and aerosol mass loadings between 10 and 40 μg m<sup>&minus;3</sup>, the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NO<sub>x</sub> conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1-MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NO<sub>x</sub> conditions and essentially nonvolatile under low-NO<sub>x</sub> conditions, owing to the higher fraction of ring-retaining products formed under low-NO<sub>x</sub> conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3–5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA.

 References Arey, J., Atkinson, R., Zielinska, B., and Mcelroy, P A.: Diurnal concentrations of volatile polycyclic aromatic-hydrocarbons and nitroarenes during a photochemical air-pollution episode in Glendora, California, Environ. Sci. Technol., 23, 321–327, 1989. Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003. Atkinson, R., Arey, J., Zielinska, B., and Aschmann, S M.: Kinetics and products of the gas-phase reactions of OH radicals and \chemN_2O_5 with naphthalene and biphenyl, Environ. Sci. Technol., 21, 1014–1022, 1987. 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 \textitm-xylene using an Aerodyne aerosol mass spectrometer, Environ. Sci. Technol., 39, 5674–5688, 2005. Bunce, N J., Liu, L., Zhu, J., and Lane, D A.: Reaction of naphthalene and its derivatives with hydroxyl radicals in the gas phase, Environ. Sci. Technol., 31, 2252–2259, 1997. Burkhardt, M R., Maniga, N I., Stedman, D H., and Paur, R J.: Gas-chromatographic method for measuring nitrogen-dioxide and peroxyacetyl nitrate in air without compressed gas-cylinders, Anal. Chem., 60, 816–819, 1988. 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. 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. 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.-Atmos., 110, \doi10.1029/2004JD005623, 2005. 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., Stone, E A., Ulbrich, I M., DeCarlo, P F., Snyder, D C., Schauer, J J., Peltier, R E., Weber, R J., Murphy, S M., Seinfeld, J H., Grover, B D., Eatough, D J., and Jimenez, J L.: Apportionment of primary and secondary organic aerosols in southern California during the 2005 Study of Organic Aerosols in Riverside (SOAR-1), Environ. Sci. Technol., 42, 7655–7662, 2008. Donahue, N M., Robinson, A L., and Pandis, S N.: Atmospheric organic particulate matter: From smoke to secondary organic aerosol, Atmos. Environ., 43, 94–106, 2009. Goldstein, A H. and Galbally, I E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007. Grieshop, A P., Donahue, N M., and Robinson, A L.: Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data, Atmos. Chem. Phys., 9, 2227–2240, 2009a. Grieshop, A P., Logue, J M., Donahue, N M., and Robinson, A L.: Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution, Atmos. Chem. Phys., 9, 1263–1277, 2009b. Heald, C L., Jacob, D J., Park, R J., Russell, L M., Huebert, B J., Seinfeld, J H., Liao, H., and Weber, R J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, \doidoi:10.1029/2005GL023831, 2005. Henze, D K., Seinfeld, J H., Ng, N L., Kroll, J H., Fu, T.-M., Jacob, D J., and Heald, C L.: Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways, Atmos. Chem. Phys., 8, 2405–2420, 2008. Jordan, C E., Ziemann, P J., Griffin, R J., Lim, Y B., Atkinson, R., and Arey, J.: Modeling SOA formation from OH reactions with C8–C17 \textitn-alkanes, Atmos. Environ., 42, 8015–8026, 2008. 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., Ng, N L., Murphy, S M., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40, 1869–1877, 2006. Kwok, E. S C. and Atkinson, R.: Estimation of hydroxyl radical reaction-rate constants for gas-phase organic-compounds using a structure-reactivity relationship – an update, Atmos. Environ., 29, 1685–1695, 1995. Lim, Y B. and Ziemann, P J.: Products and mechanism of secondary organic aerosol formation from reactions of \textitn-alkanes with OH radicals in the presence of NOx, Environ. Sci. Technol., 39, 9229–9236, 2005. Mihele, C M., Wiebe, H A., and Lane, D A.: Particle formation and gas/particle partition measurements of the products of the naphthalene-OH radical reaction in a smog chamber, Polycycl. Aromat. Comp., 22, 729–736, 2002. 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. Ng, N L., Chhabra, P S., Chan, A. W H., Surratt, J D., Kroll, J H., Kwan, A J., McCabe, D C., Wennberg, P O., Sorooshian, A., Murphy, S M., Dalleska, N F., Flagan, R C., and Seinfeld, J H.: Effect of NO<sub>x</sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, 2007a. 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, 2007b. Nishino, N., Atkinson, R., and Arey, J.: Formation of nitro products from the gas-phase OH radical-initiated reactions of toluene, naphthalene, and biphenyl: effect of \chemNO_2 concentration, Environ. Sci. Technol., 42, 9203–9209, 2008. Nishino, N., Arey, J., and Atkinson, R.: Formation and reactions of 2-Formylcinnamaldehyde in the OH radical-initiated reaction of naphthalene, Environ. Sci. Technol., 43, 1349–1353, 2009. 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. Odum, J R., Jungkamp, T. P W., Griffin, R J., Flagan, R C., and Seinfeld, J H.: The atmospheric aerosol-forming potential of whole gasoline vapor, Science, 276, 96–99, 1997. Phousongphouang, P T. and Arey, J.: Rate constants for the gas-phase reactions of a series of alkylnaphthalenes with the OH radical, Environ. Sci. Technol., 36, 1947–1952, 2002. Presto, A A., Hartz, K. E H., and Donahue, N M.: Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NO<sub>x</sub> concentration, Environ. Sci. Technol., 39, 7046–7054, 2005. Robinson, A L., Donahue, N M., Shrivastava, M K., Weitkamp, E A., Sage, A M., Grieshop, 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. 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. Sasaki, J., Aschmann, S M., Kwok, E. S C., Atkinson, R., and Arey, J.: Products of the gas-phase OH and \chemNO_3 radical-initiated reactions of naphthalene, Environ. Sci. Technol., 31, 3173–3179, 1997. 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, 3837–3855, 1996. 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, 1999a. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of emissions from air pollution sources. 1. C-1 through C-29 organic compounds from meat charbroiling, Environ. Sci. Technol., 33, 1566–1577, 1999b. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of emissions from air pollution sources. 3. C-1-C-29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35, 1716–1728, 2001. 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, 1169–1180, 2002a. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of emissions from air pollution sources. 4. C-1-C-27 organic compounds from cooking with seed oils, Environ. Sci. Technol., 36, 567–575, 2002b. Seinfeld, J H. and Pankow, J F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 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, \doi10.1029/2006GL026899, 2006. Wang, L., Atkinson, R., and Arey, J.: Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C-1- and C-2-alkylnaphthalenes, Environ. Sci. Technol., 41, 2803–2810, 2007. 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. 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, \doi10.1029/2007GL029979, 2007.