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Abstract Past and present anthropogenic mercury (Hg) release to ecosystems causes neurotoxicity and cardiovascular disease in humans with an estimated economic cost of $117 billion USD annually. Humans are primarily exposed to Hg via the consumption of contaminated freshwater and marine fish. The UNEP Minamata Convention on Hg aims to curb Hg release to the environment and is accompanied by global Hg monitoring efforts to track its success. The biogeochemical Hg cycle is a complex cascade of release, dispersal, transformation and bio-uptake processes that link Hg sources to Hg exposure. Global change interacts with the Hg cycle by impacting the physical, biogeochemical and ecological factors that control these processes. In this review we examine how global change such as biome shifts, deforestation, permafrost thaw or ocean stratification will alter Hg cycling and exposure. Based on past declines in Hg release and environmental levels, we expect that future policy impacts should be distinguishable from global change effects at the regional and global scales. 

Abstract. Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg⁰. Oxidation to water-soluble Hg^II plays a major role in Hg deposition to ecosystems. Here, we implement a new mechanism for atmospheric Hg⁰∕Hg^II redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere–ocean Hg⁰∕Hg^II cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg⁰ oxidant and that second-stage HgBr oxidation is mainly by the NO₂ and HO₂ radicals. The resulting chemical lifetime of tropospheric Hg⁰ against oxidation is 2.7 months, shorter than in previous models. Fast Hg^II atmospheric reduction must occur in order to match the  ∼ 6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM ≡ Hg⁰+Hg^II(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase Hg^II–organic complexes in aerosols and clouds, resulting in a TGM lifetime of 5.2 months against deposition and matching both mean observed TGM and its variability. Model sensitivity analysis shows that the interhemispheric gradient of TGM, previously used to infer a longer Hg lifetime against deposition, is misleading because Southern Hemisphere Hg mainly originates from oceanic emissions rather than transport from the Northern Hemisphere. The model reproduces the observed seasonal TGM variation at northern midlatitudes (maximum in February, minimum in September) driven by chemistry and oceanic evasion, but it does not reproduce the lack of seasonality observed at southern hemispheric marine sites. Aircraft observations in the lowermost stratosphere show a strong TGM–ozone relationship indicative of fast Hg⁰ oxidation, but we show that this relationship provides only a weak test of Hg chemistry because it is also influenced by mixing. The model reproduces observed Hg wet deposition fluxes over North America, Europe, and China with little bias (0–30%). It reproduces qualitatively the observed maximum in US deposition around the Gulf of Mexico, reflecting a combination of deep convection and availability of NO₂ and HO₂ radicals for second-stage HgBr oxidation. However, the magnitude of this maximum is underestimated. The relatively low observed Hg wet deposition over rural China is attributed to fast Hg^II reduction in the presence of high organic aerosol concentrations. We find that 80% of Hg^II deposition is to the global oceans, reflecting the marine origin of Br and low concentrations of organic aerosols for Hg^II reduction. Most of that deposition takes place to the tropical oceans due to the availability of HO₂ and NO₂ for second-stage HgBr oxidation.