Atmos. Chem. Phys. Discuss., 7, 14569-14601, 2007
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways
D. K. Henze1, J. H. Seinfeld1, N. L. Ng1, J. H. Kroll2, T. -M. Fu3, D. J. Jacob3, and C. L. Heald4
1Department of Chemical Engineering, California Institute of Technology, Pasadena, California, USA
2Aerodyne Research, Inc., Billerica, Massachusetts, USA
3School of Engineering and Applied Sciences and Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts, USA
4Center for Atmospheric Sciences, University of California, Berkeley, California, USA

Abstract. 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-NOx 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).

Citation: 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. Discuss., 7, 14569-14601, doi:10.5194/acpd-7-14569-2007, 2007.
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