Improved Mechanistic Model of the Atmospheric Redox Chemistry of Mercury

We present a new chemical mechanism for Hg⁰/Hg^I/Hg^II atmospheric cycling, including recent laboratory and computational data, and implement it in the GEOS-Chem global atmospheric chemistry model for comparison to observations. Our mechanism includes the oxidation of Hg⁰ by Br and OH, subsequent oxidation of Hg^I by ozone and radicals, respeciation of Hg^II in aerosols and cloud droplets, and speciated Hg^II photolysis in the gas and aqueous phases. The tropospheric Hg lifetime against deposition in the model is 5.5 months, consistent with observational constraints. The model reproduces the observed global surface Hg⁰ concentrations and Hg^II wet deposition fluxes. Br and OH make comparable contributions to global net oxidation of Hg⁰ to Hg^II. Ozone is the principal Hg^I oxidant, enabling the efficient oxidation of Hg⁰ to Hg^II by OH. BrHg^IIOH and Hg^II(OH)₂, the initial Hg^II products of Hg⁰ oxidation, respeciate in aerosols and clouds to organic and inorganic complexes, and volatilize to photostable forms. Reduction of Hg^II to Hg⁰ takes place largely through photolysis of aqueous Hg^II-organic complexes. 71% of model Hg^II deposition is to the oceans. Major uncertainties for atmospheric Hg chemistry modeling include Br concentrations, stability and reactions of Hg^I, and speciation and photoreduction of Hg^II in aerosols and clouds.