Abstract. It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a Correspondence to: A. Steffen (alexandra.steffen@ec.gc.ca) more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the Published by Copernicus Publications on behalf of the European Geosciences Union. deposited Hg does not remain in the same form in the snow. Kinetic studies undertaken have demonstrated that bromine is the major oxidant depleting Hg in the atmosphere. Modeling results demonstrate that there is a significant deposition of Hg to Polar Regions as a result of AMDEs. Models have also shown that Hg is readily transported to the Arctic from source regions, at times during springtime when this environment is actively transforming Hg from the atmosphere to the snow and ice surfaces. The presence of significant amounts of methyl Hg in snow in the Arctic surrounding AMDEs is important because this species is the link between the environment and impacts to wildlife and humans. Further, much work on methylation and demethylation processes has occurred but these processes are not yet fully understood. Recent changes in the climate and sea ice cover in Polar Regions are likely to have strong effects on the cycling of Hg in this envir...

Hg 0 + I 2 → HgI 2 Absolute N 2 , 1 atm 296 ± 1 < (1.27 ± 0.58) × 10 -19 Raofie et al. 2 M06-2X/aug-cc-pVTZ-PP High pressure limit 3.94 × 10 -14 T 1.06 e -159080/RT Auzmendi-Murua et al. 3 Hg 0 + I → HgI RRKM/B3LYP N 2 , 1 atm 180-400 4.0 × 10 -13 (T/298) -2.38 Goodsite et al. 4 Hg 0 + Br 2 → HgBr 2 Absolute Air, N 2 , 1 atm 298 ± 1 < (9 ± 2) × 10 -17 Ariya et al. 5 Absolute Air, 1 atm ∼298 No reaction detected Sumner et al. 6 Absolute Air, 1 atm 296 (6.0 ± 0.5) × 10 -17 Liu et al. 7 CCSD(T)/AVTZ 1 atm 298-2000 1.62 -9 e -110800/RT Wilcox and Okano 8 M06-2X/aug-cc-pVTZ-PP High pressure limit 4.70 × 10 -14 T 1.06 e -169190/RT Auzmendi-Murua et al. 3 Hg 0 + BrO → HgBrO Relative N 2 , 1 atm 298 10 -15 < k < 10 -13 Raofie and Ariya 9 Hg 0 + Br → HgBr Ab initio N/A, 1 atm 1.01 × 10 -12 e 1738/RT Khalizov et al. 10 RRKM/B3LYP N 2 , 1 atm 200-300 3.7 × 10 -13 (T/298) -2.76 Goodsite et al. 4 ; Goodsite et al. 11 Absolute N 2 , 0.26-0.79 atm 243-293 (1.46 ± 0.36) × 10 -32 [cm 6 molec -2 s -1 ] Donohoue et al. 12 (T/298) (-1.86±1.49) CCSD(T) Ar, 1 atm 260 1.2 × 10 -12 Shepler et al. 13 Relative Air, N 2 , 1 atm 298 ± 1 (3.2 ± 0.9) × 10 -12 Ariya et al. 5 Absolute CF 3 Br, 0.26 atm 397 ~3 × 10 -16 molec -1 s -1 Greig, G. et al. 14 CCSD(T)/AVTZ 1 atm 298-2000 6.64 × 10 -14 (T/298) -0.859 Wilcox and Okano HgBr + Br → HgBr 2 Absolute CF 3 Br, 0.26 atm 397 ~7 × 10 -14 Greig, G. et al. 14 RRKM/B3LYP N 2 , 1 atm 180-400 2.5 × 10 -10 (T/298) -0.57 Goodsite et al. 4 CCSD(T)/AVTZ 1 atm 298-2000 3.32 × 10 -12 (T/298) -9.18 Wilcox and Okano CCSD(T)/aVTZ 1 atm 298 6.33 × 10 -11 Dibble et al. 15 ; Wang et al.

Recent and historical deposition of mercury (Hg) was examined over a broad geographic area from southwestern Northwest Territories to Labrador and from the U.S. Northeast to northern Ellesmere Island using dated sediment cores from 50 lakes (18 in midlatitudes (41-50 degrees N), 14 subarctic (51-64 degrees N) and 18 in the Arctic (65-83 degrees N)). Distinct increases of Hg overtime were observed in 76% of Arctic, 86% of subarctic and 100% of midlatitude cores. Subsurface maxima in Hg depositional fluxes (microg m(-2) y(-1)) were observed in only 28% of midlatitude lakes and 18% of arctic lakes, indicating little recent reduction of inputs. Anthropogenic Hg fluxes adjusted for sediment focusing and changes in sedimentation rates (deltaF(adj,F)) ranged from -22.9 to 61 microg m(-2) y(-1) and were negatively correlated (r = -0.57, P < 0.001) with latitude. Hg flux ratios (FRs; post-1990)/pre-1850) ranged from 0.5 to 7.7. The latitudinal trend for Hg deltaF(adj,F) values showed excellent agreement with predictions of the global mercury model, GRAHM for the geographic location of each lake (r = 0.933, P < 0.001). The results are consistent with a scenario of slow atmospheric oxidation of mercury, and slow deposition of reactive mercury emissions, declining with increasing latitude away from emission sources in the midlatitudes, and support the view that there are significant anthropogenic Hg inputs in the Arctic.

Environmental context. Mercury (Hg) occurs at high concentrations in Arctic marine wildlife, posing a possible health risk to northern peoples who use these animals for food. We find that although the dramatic Hg increases in Arctic Ocean animals since pre-industrial times can be explained by sustained small annual inputs, recent rapid increases probably cannot because of the existing large oceanic Hg reservoir (the 'flywheel' effect). Climate change is a possible alternative force underpinning recent trends.Abstract. The present mercury (Hg) mass balance was developed to gain insights into the sources, sinks and processes regulating biological Hg trends in the Arctic Ocean. Annual total Hg inputs (mainly wet deposition, coastal erosion, seawater import, and 'excess' deposition due to atmospheric Hg depletion events) are nearly in balance with outputs (mainly shelf sedimentation and seawater export), with a net 0.3% year −1 increase in total mass. Marine biota represent a small fraction of the ocean's existing total Hg and methyl-Hg (MeHg) inventories. The inertia associated with these large non-biological reservoirs means that 'bottom-up' processes (control of bioavailable Hg concentrations by mass inputs or Hg speciation) are probably incapable of explaining recent biotic Hg trends, contrary to prevailing opinion. Instead, varying rates of bioaccumulation and trophic transfer from the abiotic MeHg reservoir may be key, and are susceptible to ecological, climatic and biogeochemical influences. Deep and sustained cuts to global anthropogenic Hg emissions are required to return biotic Hg levels to their natural state. However, because of mass inertia and the less dominant role of atmospheric inputs, the decline of seawater and biotic Hg concentrations in the Arctic Ocean will be more gradual than the rate of emission reduction and slower than in other oceans and freshwaters. Climate warming has likely already influenced Arctic Hg dynamics, with shrinking sea-ice cover one of the defining variables. Future warming will probably force more Hg out of the ocean's euphotic zone through greater evasion to air and faster Hg sedimentation driven by higher primary productivity; these losses will be countered by enhanced inputs from coastal erosion and rivers.

[1] An unknown fraction of mercury that is deposited onto the cryosphere is emitted back to the atmosphere. Since mercury that enters the meltwater may be converted to highly toxic bioaccumulating methylmercury, it is important to understand the physical and chemical processes that control the ultimate fate of mercury in the cryosphere. In this study, we review deposition mechanisms as well as processes whereby mercury is lost from surface snow. We then discuss redox reactions involving cryospheric mercury. We address the conditions under which reduction and oxidation occur, the stabilizing effect of halides, and the reducibility of reactive gaseous mercury versus mercury associated with particles. We discuss physical processes including the aging of the snowpack, the penetration of insolation through the cryosphere, the vertical motion of gaseous elemental mercury molecules through the cryosphere, the melting of snowpacks, and the loss of mercury from snowpacks during snowmelt both to the atmosphere and with the meltwater's ionic pulse. These physicochemical processes are universally applicable. Variations in the behavior of cryospheric mercury between open high-latitude, open high-altitude, and forested regions, which are caused by differing environmental conditions, are also discussed. Finally, we review observed concentrations of mercury in surface snow, seasonal snowpacks, meltwater, and long-term cryospheric records. The information presented here can be used to develop a parameterization of the behavior of cryospheric mercury that is dynamically linked to environmental variables.

Mercury in the Arctic is an important environmental and human health issue. The reliance of Northern Peoples on traditional foods, such as marine mammals, for subsistence means that they are particularly at risk from mercury exposure. The cycling of mercury in Arctic marine systems is reviewed here, with emphasis placed on the key sources, pathways and processes which regulate mercury levels in marine food webs and ultimately the exposure of human populations to this contaminant. While many knowledge gaps exist limiting our ability to make strong conclusions, it appears that the long range transport of mercury from Asian emissions is an important source of atmospheric Hg to the Arctic and that mercury methylation resulting in monomethylmercury production (an organic form of mercury which is both toxic and bioaccumulated) in Arctic marine waters is the principal source of mercury incorporated into food webs. Mercury concentrations in biological organisms have increased since the onset of the industrial age and are controlled by a combination of abiotic factors (e.g., monomethylmercury supply), food web dynamics and structure, and animal behavior (e.g., habitat selection and feeding behavior). Finally, although some Northern Peoples have high mercury concentrations of mercury in their blood and hair, harvesting and consuming traditional foods has many nutritional, social, cultural and physical health benefits which must be considered in risk management and communication.

Mercury and its related compounds are widely recognized as global pollutants. The accurate atmospheric modeling of its transport and fate has been the subject of much research throughout the last decade. Atmospheric gas, aqueous and heterogeneous chemistry are expected to occur for Hg-containing specie sand accurate implementation of their chemical parameters is essential for realistic modeling of mercury cycling. Although significant progress has been made, the current state of knowledge of mercury chemistry exhibits numerous uncertainties. The objective of this two-part review is to explore the sources of uncertainty from the viewpoint of mercury chemistry. In this first part, we assess the discrepancy that exists in the currently available mercury kinetic parameters for the gas and aqueous phases. Theoretical and experimental approaches of rate constant determination exhibit various levels of limitation and accuracy. We present an overview of the available techniques and the assumptions and shortcomings associated with these methods in order to assist the atmospheric modellers. We review specific mercury oxidation and reduction reactions that have been investigated and are commonly implemented in mercury models with respect to the uncertainties associated with them. We reveal that for most of these mercury reactions our current state of knowledge reflects a lack of proper under-standing of their mechanisms. Atmospheric heterogeneity is a topic of great importance and we elaborate upon it in part II of this review.

No abstract