Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 5 2007 10.5194/acpd-7-14569-2007 http://www.atmos-chem-phys-discuss.net/7/14569/2007/ http://www.atmos-chem-phys-discuss.net/7/14569/2007/acpd-7-14569-2007.html http://www.atmos-chem-phys-discuss.net/7/14569/2007/acpd-7-14569-2007.pdf 14569 14601 2007-10-15 Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways D. K. Henze daven@caltech.edu J. H. Seinfeld N. L. Ng J. H. Kroll T. -M. Fu D. J. Jacob C. L. Heald Department of Chemical Engineering, California Institute of Technology, Pasadena, California, USA Aerodyne Research, Inc., Billerica, Massachusetts, USA School of Engineering and Applied Sciences and Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts, USA Center for Atmospheric Sciences, University of California, Berkeley, California, USA Formation of SOA from the aromatic species toluene, xylene, and, for the first time, benzene, is added to a global chemical transport model. A simple mechanism is presented that accounts for competition between low and high-yield pathways of SOA formation, wherein secondary gas-phase products react further with either nitrogen oxide (NO) or hydroperoxy radical (HO₂) to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the [NO]/[HO₂] ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower [NO]/[HO₂] ratios, and the reactivity of the aromatic with respect to OH, as a lower initial reactivity allows transport away from industrial source regions, where [NO]/[HO₂] ratios are higher, to more remote regions, where this ratio is lower and, hence, the ultimate yield of SOA is higher. As a result, benzene is estimated to be the most important aromatic species with regards to formation of SOA, with a total production nearly equal that of toluene and xylene combined. In total, while only 39% percent of the aromatic species react via the low-NO_x pathway, 72% of the aromatic SOA is formed via this mechanism. Predicted SOA concentrations from aromatics in the Eastern United States and Eastern Europe are actually largest during the summer, when the [NO]/[HO₂] ratio is lower. Global production of SOA from aromatic sources is estimated at 3.5 Tg/yr, resulting in a global burden of 0.08 Tg, twice as large as previous estimates. The contribution of these largely anthropogenic sources to global SOA is still small relative to biogenic sources, which are estimated to comprise 90% of the global SOA burden, about half of which comes from isoprene. Compared to recent observations, it would appear there are additional pathways beyond those accounted for here for production of anthropogenic SOA. However, owing to differences in spatial distributions of sources and seasons of peak production, there are still regions in which aromatic SOA produced via the mechanisms identified here are predicted to contribute substantially to, and even dominate, the local SOA concentrations, such as outflow regions from North America and South East Asia during the wintertime, though total SOA concentrations there are small (~0.1 μg/m³). Andreae, M O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cy., 15, 955–966, 2001. Atkinson, R., Baulch, D L., Cox, R A., Hampson, R F., Kerr, J A., Rossi, M J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VI - IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 26, 1329–1499, 1997. Benkovitz, C M., Scholtz, M T., Pacyna, J., Tarrason, L., Dignon, J., Voldner, E C., Spiro, P A., Logan, J A., and Graedel, T E.: Global gridded inventories of anthropogenic emissions of sulfur and nitrogen, J. Geophys. Res., 101, 29 239–29 253, 1996. Bey, I., Jacob, D J., Yantosca, R M., Logan, J A., Field, B D., Fiore, A M., Li, Q B., Liu, H. G Y., Mickley, L J., and Schultz, M G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106, 23 073–23 095, 2001. Calvert, J., Atkinson, R., Becker, K H., Kamens, R M., Seinfeld, J H., Wallington, T J., and Yarwood, G.: The mechanisms of atmospheric oxidation of aromatic hyrdocarbons, Oxford University Press, New York, 2002. Chung, S H. and Seinfeld, J H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, 4407, \doi10.1029/2001JD001397, 2002. Cocker, D R., David, R., Mader, B T., Kalberer, M., Richard, C., and Seinfeld, J H.: The effect of water on gas-particle partitioning of secondary organic aerosol, II, \textitm-xylene and 1, 3, 5-trimethylbenzene photooxidation systems, Atmos. Environ., 35, 6073–6085, 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, D16305, \doi10.1029/2004JD005623, 2005. Eberhard, J. and Howard, C J.: Rate coefficients for the reactions of some C-3 to C-5 hydrocarbon peroxy radicals with NO, J. Phys. Chem. A, 101, 3360–3366, 1997. Fan, J W. and Zhang, R Y.: Atmospheric oxidation mechanism of p-xylene: A density functional theory study, J. Phys. Chem. A, 110, 7728–7737, 2006. Giglio, L., van~der Werf, G R., Randerson, J T., Collatz, G J., and Kasibhatla, P.: Global estimation of burned area using MODIS active fire observations, Atmos. Chem. Phys., 6, 957–974, 2006. 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, L18809, \doi10.1029/2005GL023831, 2005. Heald, C L., Jacob, D J., Turquety, S., Hudman, R C., Weber, R J., Sullivan, A P., Peltier, R E., Atlas, E L., de~Gouw, J A., Warneke, C., Holloway, J S., Neuman, J A., Flocke, F M., and Seinfeld, J H.: Concentrations and sources of organic carbon aerosols in the free troposphere over North America, J. Geophys. Res., 111, D23S47, doi:10.1029/2006JD007705, 2006. Henze, D K. and Seinfeld, J H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, \doi10.1029/2006GL025976, 2006. Hudman, R C., Jacob, D J., Turquety, S., Leibensperger, E M., Murray, L T., Wu, S., Gilliland, A B., Avery, M., Bertram, T H., Brune, W., Cohen, R C., Dibb, J E., Flocke, F M., Fried, A., Holloway, J., Neuman, J A., Orville, R., Perring, A., Ren, X., Sachse, G W., Singh, H B., Swanson, A., and Wooldridge, P J.: Surface and lightning sources of nitrogen oxides over the United States: magnitudes, chemical evolution, and outflow, J. Geophys. Res., 112, D12S05, \doi10.1029/2006JD007912, 2007. 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. Johnson, D., Cassanelli, P., and Cox, R A.: Isomerization of simple alkoxyl radicals: New temperature-dependent rate data and structure activity relationship, J. Phys. Chem. A, 108, 519–523, 2004. Johnson, D., Jenkin, M E., Wirtz, K., and Martin-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons, Environ. Chem., 2, 35–48, 2005. 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. Koch, R., Knispel, R., Elend, M., Siese, M., and Zetzsch, C.: Consecutive reactions of aromatic-OH adducts with NO, NO2 and O-2: benzene, naphthalene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline, Atmos. Chem. Phys., 7, 2057–2071, 2007. 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. Lack, D A., Tie, X X., Bofinger, N D., Wiegand, A N., and Madronich, S.: Seasonal variability of secondary organic aerosol: A global modeling study, J. Geophys. Res., 109, D03203, \doi10.1029/2003JD003418, 2004. Liao, H., Henze, D K., Seinfeld, J H., Wu, S., and Mickley, L J.: Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations, J. Geophys. Res., 112, D06201, \doi10.1029/2006JD007813, 2007. Lightfoot, P D., Cox, R A., Crowley, J N., Destriau, M., Hayman, G D., Jenkin, M E., Moortgat, G K., and Zabel, F.: Organic Peroxy-Radicals - Kinetics, Spectroscopy and Tropospheric Chemistry, Atmos. Environ., 26, 1805–1961, 1992. Liu, H Y., Jacob, D J., Bey, I., and Yantosca, R M.: Constraints from Pb-210 and Be-7 on wet deposition and transport in a global three-dimensional chemical tracer model driven by assimilated meteorological fields, J. Geophys. Res., 106, 12 109–12 128, 2001. Martin-Reviejo, M. and Wirtz, K.: Is benzene a precursor for secondary organic aerosol?, Environ. Sci. Technol., 39, 1045–1054, 2005. 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. Odum, J R., Jungkamp, T. P W., Griffin, R J., Forstner, H. J L., Flagan, R C., and Seinfeld, J H.: Aromatics, reformulated gasoline, and atmospheric organic aerosol formation, Environ. Sci. Technol., 31, 1890–1897, 1997. Offenberg, J H., Kleindienst, T E., Jaoui, M., Lewandowski, M., and Edney, E O.: Thermal properties of secondary organic aerosols, Geophys. Res. Lett., 33, L03816, \doi10.1029/2005GL024623, 2006. Olivier, J. G J., Bouwman, A F., Van~der Maas, C. W M., Berdowski, J. J M., Veldt, C., Bloos, J. P J., Visschedijk, A. J H., Zandveld, P. Y J., and Haverlag, J L.: Description of EDGAR Version 2.0: A set of global emission inventories of greenhous gases and ozone-depleting substances for all anthropogenic and most natural sources on a per country basis and on $1^\circ \times 1^\circ$ grid, Tech. rep., 1996. Olivier, J. G J., Bouwman, A F., Berdowski, J. J M., Veldt, C., Bloos, J. P J., Visschedijk, A. J H., Van~der Maas, C. W M., and Zandveld, P. Y J.: Sectoral emission inventories of greenhouse gases for 1990 on a per country basis as well as on 1x1 degree, Environmental Science & Policy, 2, 241–264, 1999. Park, R J., Jacob, D., Field, B D., Yantosca, R., and Chin, M.: Natural and transboundary pollution influences on sulfate-nitrate-ammonium aerosols in the United States: implications for policy, J. Geophys. Res., 109, D15204, \doi10.1029/2003JD004473, 2004. Park, R J., Jacob, D J., Kumar, N., and Yantosca, R M.: Regional visibility statistics in the United States: Natural and transboundary pollution influences, and implications for the Regional Haze Rule, Atmos. Environ., 40, 5405–5423, 2006. Pathak, R K., Presto, A A., Lane, T E., Stanier, C O., Donahue, N M., and Pandis, S N.: Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, 2007. Presto, A A. and Donahue, N M.: Investigation of α-pinene plus ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543, 2006. Presto, A A., Hartz, K. E H., and Donahue, N M.: Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NO_x concentration, Environ. Sci. Technol., 39, 7046–7054, 2005. Pun, B K. and Seigneur, C.: Investigative modeling of new pathways for secondary organic aerosol formation, Atmos. Chem. Phys., 7, 2199–2216, 2007., Song, C., Na, K S., and Cocker, D R.: Impact of the hydrocarbon to NO_x ratio on secondary organic aerosol formation, Environ. Sci. Technol., 39, 3143–3149, 2005. Surratt, J D., Kleindienst, T E., Edney, E O., Lewandowski, M., Offenberg, J H., Jaoui, M., and Seinfeld, J H.: Effect of acidity on secondary organic aerosol formation from isoprene, Environ. Sci. Technol., 41, 5363–5369, 2007. Tsigaridis, K. and Kanakidou, M.: Global modelling of secondary organic aerosol in the troposphere: a sensitivity analysis, Atmos. Chem. Phys., 3, 1849–1869, 2003. Tsigaridis, K. and Kanakidou, M.: Secondary organic aerosol importance in the future atmosphere, Atmos. Environ., 41, 4682–4692, 2007. Tsigaridis, K., Krol, M., Dentener, F J., Balkanski, Y., Lathiere, J., Metzger, S., Hauglustaine, D A., and Kanakidou, M.: Change in global aerosol composition since preindustrial times, Atmos. Chem. Phys., 6, 5143–5162, 2006. Turpin, B J. and Lim, H J.: Species contributions to PM$_2.5$ mass concentrations: Revisiting common assumptions for estimating organic mass, Aerosol. Sci. Tech., 35, 602–610, 2001. van der Werf, G R., Randerson, J T., Giglio, L., Collatz, G J., Kasibhatla, P S., and Arellano, A F.: Interannual variability in global biomass burning emissions from 1997 to 2004, Atmos. Chem. Phys., 6, 3423–3441, 2006. van Donkelaar, A., Martin, R V., Park, R J., Heald, C L., Fu, T.-M., Liao, H., and Guenther, A.: Model evidence for a significant source of secondary organic aerosol from isoprene, Atmos. Environ., 41, 1267–1274, 2007. van Noije, T. P C., Eskes, H J., Dentener, F J., Stevenson, D S., Ellingsen, K., Schultz, M G., Wild, O., Amann, M., Atherton, C S., Bergmann, D J., Bey, I., Boersma, K F., Butler, T., Cofala, J., Drevet, J., Fiore, A M., Gauss, M., Hauglustaine, D A., Horowitz, L W., Isaksen, I. S A., Krol, M C., Lamarque, J F., Lawrence, M G., Martin, R V., Montanaro, V., Muller, J F., Pitari, G., Prather, M J., Pyle, J A., Richter, A., Rodriguez, J M., Savage, N H., Strahan, S E., Sudo, K., Szopa, S., and van Roozendael, M.: Multi-model ensemble simulations of tropospheric NO₂ compared with GOME retrievals for the year 2000, Atmos. Chem. Phys., 6, 2943–2979, 2006. Volkamer, R., Klotz, B., Barnes, I., Imamura, T., Wirtz, K., Washida, N., Becker, K H., and Platt, U.: OH-initiated oxidation of benzene – Part I. Phenol formation under atmospheric conditions, Phys. Chem. Chem. Phys., 4, 1598–1610, 2002. 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, \doi10.1029/2006GL02689, 2006. Wang, Y H., Jacob, D J., and Logan, J A.: Global simulation of tropospheric O-3-NOx-hydrocarbon chemistry 1. Model formulation, J. Geophys. Res., 103, 10 713–10 725, 1998. Wang, Y X., McElroy, M B., Martin, R V., Streets, D G., Zhang, Q., and Fu, T M.: Seasonal variability of NO_x emissions over east China constrained by satellite observations: Implications for combustion and microbial sources, J. Geophys. Res., 112, D06301, \doi10.1029/2006JD007538, 2007. Warneke, C., McKeen, S A., de~Gouw, J A., Goldan, P D., Kuster, W C., Holloway, J S., Williams, E J., Lerner, B M., Parrish, D D., Trainer, M., Fehsenfeld, F C., Kato, S., Atlas, E L., Baker, A., and Blake, D R.: Determination of urban volatile organic compound emission ratios and comparison with an emissions database, J. Geophys. Res., 112, D10S47, \doi10.1029/2006JD007930, 2007. Wesely, M L.: Parameterization of Surface Resistances to Gaseous Dry Deposition in Regional-Scale Numerical-Models, Atmos. Environ., 23, 1293–1304, 1989. Zhang, Y., Huang, J.-P., Henze, D K., and Seinfeld, J H.: The role of isoprene in secondary organic aerosol formation on a regional scale, J. Geophys. Res., 112, D06201, doi:10.1029/2006JD007813, 2007. Zhao, J., Zhang, R Y., Misawa, K., and Shibuya, K.: Experimental product study of the OH-initiated oxidation of m-xylene, J Photoch Photobio A, 176, 199–207, 2005.