A theoretical study was performed involving the reactions of a series of atmospherically significant Criegee intermediates (CIs), including parent, mono-and dimethyl -substituted CIs, with water and the water dimer at the CCSD(T)//B3LYP/6-311+G(2d,2p) level. We investigated two reaction routes leading to α-hydroxyalkyl hydroperoxide (HAHP). According to our calculations, the most favorable route is the formation of HAHP as the result of reactions of CIs with the water dimer. The rate constants for both pathways were calculated and the dependence of overall rate constant on temperature and relative humidity was also evaluated. The implication of our results to the chemistry of the troposphere is herein discussed.

Mercury is a persistent, toxic and bio-accumulative pollutant of global interest. Its main mass in the troposphere is in the form of elemental gas-phase mercury. Rapid, near-complete depletion of mercury has been observed during spring in the atmospheric boundary layer of frozen marine areas in Arctic, sub-Arctic and Antarctic locations. It is strongly correlated with ozone depletion. To date, evidence has indicated strongly that chemistry involving halogen gases from surface sea-salt is the mechanism of this destruction. Precisely which halogen gases are the main players has remained unresolved. Our novel kinetic data and multiscale modelling show that Br atoms and BrO radicals are the most effective halogens driving mercury oxidation. The reduction of oxidized mercury deposited in the snow pack back to Hg⁰ and subsequent diffusion to the atmosphere is observed. However, it cannot compensate for the total deposition, and a net accumulation occurs. We use a unique global atmospheric mercury model to estimate that halogen-driven mercury depletion events result in a 44% increase in the net deposition of mercury to the Arctic. Over a 1-yr cycle, we estimate an accumulation of 325 tons of mercury in the Arctic

A B S T R A C TMercury is a persistent, toxic and bio-accumulative pollutant of global interest. Its main mass in the troposphere is in the form of elemental gas-phase mercury. Rapid, near-complete depletion of mercury has been observed during spring in the atmospheric boundary layer of frozen marine areas in Arctic, sub-Arctic and Antarctic locations. It is strongly correlated with ozone depletion. To date, evidence has indicated strongly that chemistry involving halogen gases from surface sea-salt is the mechanism of this destruction. Precisely which halogen gases are the main players has remained unresolved. Our novel kinetic data and multiscale modelling show that Br atoms and BrO radicals are the most effective halogens driving mercury oxidation. The reduction of oxidized mercury deposited in the snow pack back to Hg 0 and subsequent diffusion to the atmosphere is observed. However, it cannot compensate for the total deposition, and a net accumulation occurs. We use a unique global atmospheric mercury model to estimate that halogen-driven mercury depletion events result in a 44% increase in the net deposition of mercury to the Arctic. Over a 1-yr cycle, we estimate an accumulation of 325 tons of mercury in the Arctic.

Abstract. L. Zhang et al. (2012), in a recent report, compared model estimates with new observations of oxidized and particulate mercury species (Hg2+ and Hgp) in the Great Lakes region and found that the sum of Hg2+ and Hgp varied between a factor of 2 to 10 between measurements and model. They suggested too high emission inputs as Hg2+ and too fast oxidative conversion of Hg0 to Hg2+ and Hgp as possible causes. This study quantitatively explores measurement uncertainties in detail. These include sampling efficiency, composition of sample, interfering species and calibration errors. Model (Global/Regional Atmospheric Heavy Metals Model – GRAHM) sensitivity experiments are used to examine the consistency between various Hg measurements and speciation of Hg near emission sources to better understand the discrepancies between modelled and measured concentrations of Hg2+ and Hgp. We find that the ratio of Hg0, Hg2+ and Hgp in the emission inventories, measurements of surface air concentrations of oxidized Hg and measurements of wet deposition are currently inconsistent with each other in the vicinity of emission sources. Current speciation of Hg emissions suggests higher concentrations of Hg2+ in air and in precipitation near emission sources; however, measured air concentrations of Hg2+ and measured concentrations of Hg in precipitation are not found to be significantly elevated near emission sources compared to the remote regions. The averaged unbiased root mean square error (RMSE) between simulated and observed concentrations of Hg2+ is found to be reduced by 42% and for Hgp reduced by 40% for 21 North American sites investigated, when a ratio for Hg0 : Hg2+ : Hgp in the emissions is changed from 50 : 40 : 10 (as specified in the original inventories) to 90 : 8 : 2. Unbiased RMSE reductions near emissions sources in the eastern United States and Canada are found to be reduced by up to 58% for Hg2+. Significant improvement in the model simulated spatial distribution of wet deposition of mercury in North America is noticed with the modified Hg emission speciation. Measurement-related uncertainties leading to lower estimation of Hg2+ concentrations are 86%. Uncertainties yielding either to higher or lower Hg2+ concentrations are found to be 36%. Finally, anthropogenic emission uncertainties are 106% for Hg2+. Thus it appears that the identified uncertainties for model estimates related to mercury speciation near sources, uncertainties in measurement methodology and uncertainties in emissions can close the gap between modelled and observed estimates of oxidized mercury found in L. Zhang et al. (2012). Model sensitivity simulations show that the measured concentrations of oxidized mercury, in general, are too low to be consistent with measured wet deposition fluxes in North America. Better emission inventories (with respect to speciation), better techniques for measurements of oxidized species and knowledge of mercury reduction reactions in different environments (including in-plume) in all phases are needed for improving the mercury models.

Abstract. An unknown fraction of mercury that is deposited onto snowpacks is revolatilized to the atmosphere. Determining the revolatilized fraction is important since mercury that enters the snowpack meltwater may be converted to highly toxic bioaccumulating methylmercury. In this study, we present a new dynamic physically-based snowpack/meltwater model for mercury that is suitable for large-scale atmospheric models for mercury. It represents the primary physical and chemical processes that determine the fate of mercury deposited onto snowpacks. The snowpack/meltwater model was implemented in Environment Canada's atmospheric mercury model GRAHM. For the first time, observed snowpack-related mercury concentrations are used to evaluate and constrain an atmospheric mercury model. We find that simulated concentrations of mercury in both snowpacks and the atmosphere's surface layer agree closely with observations. The simulated concentration of mercury in both in the top 30 cm and the top 150 cm of the snowpack, averaged over 2005-2009, is predominantly below 6 ng L −1 over land south of 66.5°N but exceeds 18 ng L −1 over sea ice in extensive areas of the Arctic Ocean and Hudson Bay. The average simulated concentration of mercury in snowpack meltwater runoff tends to be higher on the Russian/European side (>20 ng L −1 ) of the Arctic Ocean than on the Canadian side (<10 ng L −1 ). The correlation coefficient between observed and simulated monthly mean atmospheric surface-level gaseous elemental mercury (GEM) concentrations increased significantly with the inclusion of the new snowpack/meltwater model at two of the three stations (midlatitude, subarctic) studied and remained constant at the third (arctic). Oceanic emissions are postulated to produce the observed summertime maximum in concentrations of surface-level atmospheric GEM at Alert in the Canadian Arctic and to generate the summertime volatility observed in these concentrations at both Alert and Kuujjuarapik on subarctic Hudson Bay, Canada. We find that the fraction of deposited mercury that is revolatilized from snowpacks increases with latitude from 39 % between 30 and 45°N, to 57 % from 45 to 60°N, 67 % from 60 to 66.5°N, and 75 % polewards of 66.5°N on an annual basis. Combining this latitudinal gradient with the latitudinally increasing coverage of snowpacks causes yearly net deposition as a fraction of gross deposition to decrease from 98 % between 30 and 45°N to 89 % between 45 and 60°N, 73 % between 60 and 66.5°N, and 44 % within the Arctic Circle. The yearly net deposition and net accumulation of mercury at the surface within the Arctic Circle north of 66.5°N are estimated at 153 and 117 Mg, respectively. We calculate that 58 and 50 Mg of mercury are deposited annually to the Arctic Ocean directly and indirectly via melting snowpacks, respectively. For terrestrial surfaces within the Arctic Circle, we find that 29 and 16 Mg of mercury are deposited annually directly and indirectly via melting snowpacks, respectively. Within the Arctic Circle, multi-s...