Anthropogenic short-lived halogens increase human exposure to mercury contamination due to enhanced mercury oxidation over continents.

Mercury (Hg) is a contaminant of global concern, and an accurate understanding of its atmospheric fate is needed to assess its risks to humans and ecosystem health. Atmospheric oxidation of Hg is key to the deposition of this toxic metal to the Earth's surface. Short-lived halogens (SLHs) can provide halogen radicals to directly oxidize Hg and perturb the budget of other Hg oxidants (e.g., OH and O3). In addition to known ocean emissions of halogens, recent observational evidence has revealed abundant anthropogenic emissions of SLHs over continental areas. However, the impacts of anthropogenic SLHs emissions on the atmospheric fate of Hg and human exposure to Hg contamination remain unknown. Here, we show that the inclusion of anthropogenic SLHs substantially increased local Hg oxidation and, consequently, deposition in/near Hg continental source regions by up to 20%, thereby decreasing Hg export from source regions to clean environments. Our modeling results indicated that the inclusion of anthropogenic SLHs can lead to higher Hg exposure in/near Hg source regions than estimated in previous assessments, e.g., with increases of 8.7% and 7.5% in China and India, respectively, consequently leading to higher Hg-related human health risks. These results highlight the urgent need for policymakers to reduce local Hg and SLHs emissions. We conclude that the substantial impacts of anthropogenic SLHs emissions should be included in model assessments of the Hg budget and associated health risks at local and global scales.

Arctic atmospheric mercury: Sources and changes.

Global anthropogenic and legacy mercury (Hg) emissions are the main sources of Arctic Hg contamination, primarily transported there via the atmosphere. This review summarizes the state of knowledge of the global anthropogenic sources of Hg emissions, and examines recent changes and source attribution of Hg transport and deposition to the Arctic using models. Estimated global anthropogenic Hg emissions to the atmosphere for 2015 were ~2220 Mg, ~20% higher than 2010. Global anthropogenic, legacy and geogenic Hg emissions were, respectively, responsible for 32%, 64% (wildfires: 6-10%) and 4% of the annual Arctic Hg deposition. Relative contributions to Arctic deposition of anthropogenic origin was dominated by sources in East Asia (32%), Commonwealth of Independent States (12%), and Africa (12%). Model results exhibit significant spatiotemporal variations in Arctic anthropogenic Hg deposition fluxes, driven by regional differences in Hg air transport routes, surface and precipitation uptake rates, and inter-seasonal differences in atmospheric circulation and deposition pathways. Model simulations reveal that changes in meteorology are having a profound impact on contemporary atmospheric Hg in the Arctic. Reversal of North Atlantic Oscillation phase from strongly negative in 2010 to positive in 2015, associated with lower temperature and more sea ice in the Canadian Arctic, Greenland and surrounding ocean, resulted in enhanced production of bromine species and Hg(0) oxidation and lower evasion of Hg(0) from ocean waters in 2015. This led to increased Hg(II) (and its deposition) and reduced Hg(0) air concentrations in these regions in line with High Arctic observations. However, combined changes in meteorology and anthropogenic emissions led to overall elevated modeled Arctic air Hg(0) levels in 2015 compared to 2010 contrary to observed declines at most monitoring sites, likely due to uncertainties in anthropogenic emission speciation, wildfire emissions and model representations of air-surface Hg fluxes.

Photochemistry of oxidized Hg(I) and Hg(II) species suggests missing mercury oxidation in the troposphere.

Mercury (Hg), a global contaminant, is emitted mainly in its elemental form Hg0 to the atmosphere where it is oxidized to reactive HgII compounds, which efficiently deposit to surface ecosystems. Therefore, the chemical cycling between the elemental and oxidized Hg forms in the atmosphere determines the scale and geographical pattern of global Hg deposition. Recent advances in the photochemistry of gas-phase oxidized HgI and HgII species postulate their photodissociation back to Hg0 as a crucial step in the atmospheric Hg redox cycle. However, the significance of these photodissociation mechanisms on atmospheric Hg chemistry, lifetime, and surface deposition remains uncertain. Here we implement a comprehensive and quantitative mechanism of the photochemical and thermal atmospheric reactions between Hg0, HgI, and HgII species in a global model and evaluate the results against atmospheric Hg observations. We find that the photochemistry of HgI and HgII leads to insufficient Hg oxidation globally. The combined efficient photoreduction of HgI and HgII to Hg0 competes with thermal oxidation of Hg0, resulting in a large model overestimation of 99% of measured Hg0 and underestimation of 51% of oxidized Hg and ∼66% of HgII wet deposition. This in turn leads to a significant increase in the calculated global atmospheric Hg lifetime of 20 mo, which is unrealistically longer than the 3-6-mo range based on observed atmospheric Hg variability. These results show that the HgI and HgII photoreduction processes largely offset the efficiency of bromine-initiated Hg0 oxidation and reveal missing Hg oxidation processes in the troposphere.

Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition.

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.

Intercomparison study of atmospheric mercury models: 2. Modelling results vs. long-term observations and comparison of country deposition budgets.

Five regional scale models with a horizontal domain covering the European continent and its surrounding seas, two hemispheric and one global scale model participated in the atmospheric Hg modelling intercomparison study. The models were compared between each other and with available measurements from 11 monitoring stations of the EMEP measurement network. Because only a very limited number of long-term measurement records of Hg were available, significant attention was given to the intercomparison of modelling results. Monthly and annually averaged values of Hg concentrations and depositions as well as items of the Hg deposition budgets for individual European countries were compared. The models demonstrated good agreement (within +/-20%) between annual modelled and observed values of gaseous elemental Hg. Modelled values of Hg wet deposition in Western and Central Europe agreed with the observations within +/-45%. The probability to predict wet depositions within a factor of 2 with regard to measurements was 50-70% for all the models. The scattering of modelling results for dry depositions of Hg was more significant (up to +/-50% at the annual scale and even higher for monthly data). Contribution of dry deposition to the total Hg deposition was estimated at 20-30% with elevated dry deposition fluxes during summer time. The participating models agree in their predictions of transboundary pollution for individual countries within +/-60% at the monthly scale and within +/-30% at the annual scale. For the cases investigated, all the models predict that the major part of national anthropogenic Hg emissions is transported outside the country territory.