Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs. low-yield pathways

Article, Other literature type English OPEN
Henze , D. K. ; Seinfeld , J. H. ; Ng , N. L. ; Kroll , J. H. ; Fu , T.-M. ; Jacob , D. J. ; Heald , C. L. (2008)
  • Publisher: European Geosciences Union
  • Journal: (issn: 1680-7324, eissn: 1680-7324)
  • Related identifiers: doi: 10.5194/acp-8-2405-2008, doi: 10.5194/acp-8-2405-2008.
  • Subject: Chemistry | [ SDU.OCEAN ] Sciences of the Universe [physics]/Ocean, Atmosphere | QD1-999 | Physics | Caltech Library Services | QC1-999

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 nitric oxide (NO) or hydroperoxy radical (HO<sub>2</sub>) to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the [NO]/[HO<sub>2</sub>] ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower [NO]/[HO<sub>2</sub>] 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]/[HO<sub>2</sub>] 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 global formation of SOA, with a total production nearly equal that of toluene and xylene combined. Global production of SOA from aromatic sources via the mechanisms identified here 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. Uncertainty in these estimates owing to factors ranging from the atmospheric relevance of chamber conditions to model deficiencies result in an estimated range of SOA production from aromatics of 2–12 Tg/yr. Though this uncertainty range affords a significant anthropogenic contribution to global SOA, it is evident from comparisons to recent observations that additional pathways for production of anthropogenic SOA still exist beyond those accounted for here. Nevertheless, owing to differences in spatial distributions of sources and seasons of peak production, regions exist 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 modeled SOA concentrations there are small (~0.1 μg/m<sup>3</sup>).
  • References (84)
    84 references, page 1 of 9

    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.

    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, http://www.atmos-chem-phys.net/7/4135/2007/.

    Chung, S. H. and Seinfeld, J. H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, 4407, doi:10.1029/2001JD001397, 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, m-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, doi:10.1029/2004JD005623, 2005.

    de Gouw, J. A., Brock, C. A., Atlas, E. L., Bates, T. S., Fehsenfeld, F. C., Goldan, P. D., Holloway, J. S., Kuster, W. C., Lerner, B. M., Mattew, B. M., Middlebrook, A. M., Onasch, T. B., Peltier, R. E., Quinn, P. K., Senff, C. J., Stohl, A., Sullivan, A. P., Trainer, M., Warneke, C., Weber, R. J., and Williams, E. J.: Sources of particulate matter in the Northeastern United States: 1. Direct emissions and secondary formation of organic matter in urban plumes, J. Geophys. Res., 113, D08301, doi:10.1029/2007JD009243, 2008.

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