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A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer

Abstract

RECENT measurements of inorganic chlorine gases1 and hydrocarbons2 indicate the presence of reactive chlorine in the remote marine boundary layer; reactions involving chlorine and bromine can affect the concentrations of ozone, hydrocarbons and cloud condensation nuclei. The known formation mechanisms of reactive halogens require significant concentrations of nitrogen oxides3–5, which are not present in the unpolluted air of the remote marine boundary layer6. Here we propose an autocatalytic mechanism for halogen release from sea-salt aerosol: gaseous HOBr is scavenged by the aerosol and converted to only slightly soluble BrCl and Br2, which are released into the gas phase. Depending on the sea-salt concentration and given a boundary layer that is stable for a few days, gaseous HOCl and HOBr may reach molar mixing ratios of up to 35 pmol mol−1. We calculate that HOBr and HOCl are responsible for 20% and 40%, respectively, of the sulphur (IV) oxidation7,8 that occurs in the aerosol phase. The additional S(IV) oxidation reduces the formation of cloud-condensation nuclei, and hence the feedback between greenhouse warming, oceanic DMS emission and cloud albedo. We also calculate significant bromine-catalysed ozone loss.

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Vogt, R., Crutzen, P. & Sander, R. A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer. Nature 383, 327–330 (1996). https://doi.org/10.1038/383327a0

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