A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer
Item
Title (Dublin Core)
A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer
Description (Dublin Core)
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 description of oxidative degradation of up to C<sub>3</sub>-hydrocarbons (CH<sub>4</sub>, C<sub>2</sub>H<sub>6</sub>, C<sub>3</sub>H<sub>8</sub>, C<sub>2</sub>H<sub>4</sub>, C<sub>3</sub>H<sub>6</sub>, and C<sub>2</sub>H<sub>2</sub>) initiated by reactions with OH radicals, Cl- and Br-atoms, and O<sub>3</sub>. 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 forming 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 (CH<sub>3</sub>CHO) and alkenes (especially C<sub>3</sub>H<sub>6</sub>) 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 a 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. The reaction between Br atoms and C<sub>2</sub>H<sub>2</sub> is shown to be unimportant for determining the degree of bromine activation in the remote MBL. 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, NO<sub>x</sub>, and O<sub>3</sub> in the MBL.
Creator (Dublin Core)
Toyota, K.
Kanaya, Y.
Takahashi, M.
Akimoto, H.
Date (Dublin Core)
2018-06-28
Type (Dublin Core)
Text
Format (Dublin Core)
application/pdf
Identifier (Dublin Core)
10.5194/acp-4-1961-2004
https://acp.copernicus.org/articles/4/1961/2004/
Source (Dublin Core)
eISSN: 1680-7324
Language (Dublin Core)
eng
