We present a new chemical mechanism for Hg0/HgI/HgII 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 HgI by ozone and radicals, respeciation of HgII in aerosols and cloud droplets, and speciated HgII 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 HgII wet deposition fluxes. Br and OH make comparable contributions to global net oxidation of Hg0 to HgII. Ozone is the principal HgI oxidant, enabling the efficient oxidation of Hg0 to HgII by OH. BrHgIIOH and HgII(OH)2, the initial HgII products of Hg0 oxidation, respeciate in aerosols and clouds to organic and inorganic complexes, and volatilize to photostable forms. Reduction of HgII to Hg0 takes place largely through photolysis of aqueous HgII–organic complexes. 71% of model HgII deposition is to the oceans. Major uncertainties for atmospheric Hg chemistry modeling include Br concentrations, stability and reactions of HgI, and speciation and photoreduction of HgII in aerosols and clouds.

Anthropogenic mercury (Hg(0)) emissions oxidize to gaseous Hg(II) compounds, before deposition to Earth surface ecosystems. Atmospheric reduction of Hg(II) competes with deposition, thereby modifying the magnitude and pattern of Hg deposition. Global Hg models have postulated that Hg(II) reduction in the atmosphere occurs through aqueous-phase photoreduction that may take place in clouds. Here we report that experimental rainfall Hg(II) photoreduction rates are much slower than modelled rates. We compute absorption cross sections of Hg(II) compounds and show that fast gas-phase Hg(II) photolysis can dominate atmospheric mercury reduction and lead to a substantial increase in the modelled, global atmospheric Hg lifetime by a factor two. Models with Hg(II) photolysis show enhanced Hg(0) deposition to land, which may prolong recovery of aquatic ecosystems long after Hg emissions are lowered, due to the longer residence time of Hg in soils compared with the ocean. Fast Hg(II) photolysis substantially changes atmospheric Hg dynamics and requires further assessment at regional and local scales.

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When released to the biosphere, mercury (Hg) is very mobile and can take millennia to be returned to a secure, long-term repository. Understanding where and when Hg was released as a result of human activities allows better quantification of present-day reemissions and future trajectories of environmental concentrations. In this work, we estimate the time-varying releases of Hg in seven world regions over the 500 year period, 1510-2010. By our estimation, this comprises 95% of all-time anthropogenic releases. Globally, 1.47 Tg of Hg were released in this period, 23% directly to the atmosphere and 77% to land and water bodies. Cumulative releases have been largest in Europe (427 Gg) and North America (413 Gg). In some world regions (Africa/Middle East and Oceania), almost all (>99%) of the Hg is relatively recent (emitted since 1850), whereas in South America it is mostly of older vintage (63% emitted before 1850). Asia was the greatest-emitting region in 2010, while releases in Europe and North America have declined since the 1970s, as recognition of the risks posed by Hg have led to its phase-out in commercial usage. The continued use of Hg in artisanal and small-scale gold mining means that the Africa/Middle East region is now a major contributor. We estimate that 72% of cumulative Hg emissions to air has been in the form of elemental mercury (Hg 0 ), which has a long lifetime in the atmosphere and can therefore be transported long distances. Our results show that 83% of the total Hg has been released to local water bodies, onto land, or quickly deposited from the air in divalent (Hg II ) form. Regionally, this value ranges from 77% in Africa/ Middle East and Oceania to 89% in South America. Results from global biogeochemical modeling indicate improved agreement of the refined emission estimates in this study with archival records of Hg accumulation in estuarine and deep ocean sediment.