Mercury (Hg) is a global pollutant that affects human and ecosystem health. We synthesize understanding of sources, atmosphere-land-ocean Hg dynamics and health effects, and consider the implications of Hg-control policies. Primary anthropogenic Hg emissions greatly exceed natural geogenic sources, resulting in increases in Hg reservoirs and subsequent secondary Hg emissions that facilitate its global distribution. The ultimate fate of emitted Hg is primarily recalcitrant soil pools and deep ocean waters and sediments. Transfers of Hg emissions to largely unavailable reservoirs occur over the time scale of centuries, and are primarily mediated through atmospheric exchanges of wet/dry deposition and evasion from vegetation, soil organic matter and ocean surfaces. A key link between inorganic Hg inputs and exposure of humans and wildlife is the net production of methylmercury, which occurs mainly in reducing zones in freshwater, terrestrial, and coastal environments, and the subsurface ocean. Elevated human exposure to methylmercury primarily results from consumption of estuarine and marine fish. Developing fetuses are most at risk from this neurotoxin but health effects of highly exposed populations and wildlife are also a concern. Integration of Hg science with national and international policy efforts is needed to target efforts and evaluate efficacy.

http://pubs.acs.org/doi/pdf/10.1021/es305071v

Mercury as a Global Pollutant: Sources, Pathways, and Effects

Mercury pollution poses global human health and environmental risks. Although mercury is naturally present in the environment, human activities, such as coal burning, have increased the amount of mercury cycling among the land, atmosphere, and ocean by a factor of three to five. Emitted to the atmosphere in its elemental form, mercury travels worldwide before oxidizing to a form that deposits to ecosystems. In aquatic systems, mercury can convert into methylmercury, a potent neurotoxin. People and wildlife are exposed to methylmercury as it bioaccumulates up the food chain. Mercury continues to circulate in the atmosphere, oceans, and terrestrial system for centuries to millennia before it returns to deep-ocean sediments. Areas of uncertainty in the global biogeochemical cycle of mercury include oxidation processes in the atmosphere, land-atmosphere and ocean-atmosphere cycling, and methylation processes in the ocean. National and international policies have addressed direct mercury emissions, but further...

Global Biogeochemical Cycling of Mercury: A Review

https://escholarship.org/content/qt8mf445sh/qt8mf445sh.pdf?t=nu02or

Atmospheric composition change – global and regional air quality

. During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

/pdf/halogens-and-their-role-in-polar-boundary-layer-ozone-3v9c7c6k0c.pdf

Halogens and their role in polar boundary-layer ozone depletion

Atmospheric aerosols can be categorized into primary particles, which are directly emitted by their sources, and secondary particles, generated in the atmosphere from gaseous inorganic and organic precursors. For example, atmospheric oxidation of sulfur containing compounds leads to sulfuric acid and its salts, which represent a major secondary inorganic component of atmospheric aerosols. Likewise, oxidation of nitrogen oxides leads to nitric acid or its salts, which are also abundant in aerosols. The ocean surface, which covers three-quarters of the planet, offers a remarkably dynamic and chemically complex surface for interfacial reactions in the marine boundary layer. The porous nature of permanent or perennial snowpacks adds a tremendous amount of surface area, with which the atmosphere interacts. In short, solar radiation can provide the energy to initiate reactions while atmospherically available surfaces or condensed phases may act to reduce the required energy for a given photochemical pathway, for instance, by allowing a longer wavelength for reaction of species associated with a surface or bulk phase environment.

Heterogeneous photochemistry in the atmosphere.

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 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 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 environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes.

/pdf/a-synthesis-of-atmospheric-mercury-depletion-event-chemistry-25nq37zth4.pdf

A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow

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 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 the history of Hg in Polar Regions, 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 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 roles that the snow pack, oceans, fresh water and the sea ice play in the cycling of Hg are 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 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 have occurred but 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 environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes Mercury, Atmospheric mercury depletion events (AMDE), Polar, Arctic, Antarctic, Ice

F. Cobbett

Papers

A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow

A synthesis of atmospheric mercury depletion event chemistry linking atmosphere, snow and water