Atmos. Chem. Phys. Discuss., 3, 4549-4632, 2003
www.atmos-chem-phys-discuss.net/3/4549/2003/
doi:10.5194/acpd-3-4549-2003
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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.
A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer
K. Toyota1, Y. Kanaya1, M. Takahashi1,2, and H. Akimoto1
1Frontier Research System for Global Change, Yokohama, Japan
2Also at Center for Climate System Research, The University of Tokyo, Tokyo, Japan

Abstract. A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.

Citation: Toyota, K., Kanaya, Y., Takahashi, M., and Akimoto, H.: A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer, Atmos. Chem. Phys. Discuss., 3, 4549-4632, doi:10.5194/acpd-3-4549-2003, 2003.
 
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