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 biogeochemical cycling in the ocean and policy implications.

We review recent progress in our understanding of the global cycling of mercury (Hg), including best estimates of Hg concentrations and pool sizes in major environmental compartments and exchange processes within and between these reservoirs. Recent advances include the availability of new global datasets covering areas of the world where environmental Hg data were previously lacking; integration of these data into global and regional models is continually improving estimates of global Hg cycling. New analytical techniques, such as Hg stable isotope characterization, provide novel constraints of sources and transformation processes. The major global Hg reservoirs that are, and continue to be, affected by anthropogenic activities include the atmosphere (4.4–5.3 Gt), terrestrial environments (particularly soils: 250–1000 Gg), and aquatic ecosystems (e.g., oceans: 270–450 Gg). Declines in anthropogenic Hg emissions between 1990 and 2010 have led to declines in atmospheric Hg0 concentrations and HgII wet deposition in Europe and the US (− 1.5 to − 2.2% per year). Smaller atmospheric Hg0 declines (− 0.2% per year) have been reported in high northern latitudes, but not in the southern hemisphere, while increasing atmospheric Hg loads are still reported in East Asia. New observations and updated models now suggest high concentrations of oxidized HgII in the tropical and subtropical free troposphere where deep convection can scavenge these HgII reservoirs. As a result, up to 50% of total global wet HgII deposition has been predicted to occur to tropical oceans. Ocean Hg0 evasion is a large source of present-day atmospheric Hg (approximately 2900 Mg/year; range 1900–4200 Mg/year). Enhanced seawater Hg0 levels suggest enhanced Hg0 ocean evasion in the intertropical convergence zone, which may be linked to high HgII deposition. Estimates of gaseous Hg0 emissions to the atmosphere over land, long considered a critical Hg source, have been revised downward, and most terrestrial environments now are considered net sinks of atmospheric Hg due to substantial Hg uptake by plants. Litterfall deposition by plants is now estimated at 1020–1230 Mg/year globally. Stable isotope analysis and direct flux measurements provide evidence that in many ecosystems Hg0 deposition via plant inputs dominates, accounting for 57–94% of Hg in soils. Of global aquatic Hg releases, around 50% are estimated to occur in China and India, where Hg drains into the West Pacific and North Indian Oceans. A first inventory of global freshwater Hg suggests that inland freshwater Hg releases may be dominated by artisanal and small-scale gold mining (ASGM; approximately 880 Mg/year), industrial and wastewater releases (220 Mg/year), and terrestrial mobilization (170–300 Mg/year). For pelagic ocean regions, the dominant source of Hg is atmospheric deposition; an exception is the Arctic Ocean, where riverine and coastal erosion is likely the dominant source. Ocean water Hg concentrations in the North Atlantic appear to have declined during the last several decades but have increased since the mid-1980s in the Pacific due to enhanced atmospheric deposition from the Asian continent. Finally, we provide examples of ongoing and anticipated changes in Hg cycling due to emission, climate, and land use changes. It is anticipated that future emissions changes will be strongly dependent on ASGM, as well as energy use scenarios and technology requirements implemented under the Minamata Convention. We predict that land use and climate change impacts on Hg cycling will be large and inherently linked to changes in ecosystem function and global atmospheric and ocean circulations. Our ability to predict multiple and simultaneous changes in future Hg global cycling and human exposure is rapidly developing but requires further enhancement.

/pdf/a-review-of-global-environmental-mercury-processes-in-2yqze7953z.pdf

A review of global environmental mercury processes in response to human and natural perturbations: Changes of emissions, climate, and land use

Understanding the biogeochemical cycling of mercury is critical for explaining the presence of mercury in remote regions of the world, such as the Arctic and the Himalayas, as well as local concentrations. While we have good knowledge of present-day fluxes of mercury to the atmosphere, we have little knowledge of what emission levels were like in the past. Here we develop a trend of anthropogenic emissions of mercury to the atmosphere from 1850 to 2008-for which relatively complete data are available-and supplement that trend with an estimate of anthropogenic emissions prior to 1850. Global mercury emissions peaked in 1890 at 2600 Mg yr(-1), fell to 700-800 Mg yr(-1) in the interwar years, then rose steadily after 1950 to present-day levels of 2000 Mg yr(-1). Our estimate for total mercury emissions from human activities over all time is 350 Gg, of which 39% was emitted before 1850 and 61% after 1850. Using an eight-compartment global box-model of mercury biogeochemical cycling, we show that these emission trends successfully reproduce present-day atmospheric enrichment in mercury.

/pdf/all-time-releases-of-mercury-to-the-atmosphere-from-human-33lo071aep.pdf

All-Time Releases of Mercury to the Atmosphere from Human Activities

[1] Elevated mercury (Hg) in marine and terrestrial ecosystems is a global health concern because of the formation of toxic methylmercury. Humans have emitted Hg to the atmosphere for millennia, and this Hg has deposited and accumulated into ecosystems globally. Here we present a global biogeochemical model with fully coupled atmospheric, terrestrial, and oceanic Hg reservoirs to better understand human influence on Hg cycling and timescales for responses. We drive the model with a historical inventory of anthropogenic emissions from 2000 BC to present. Results show that anthropogenic perturbations introduced to surface reservoirs (atmosphere, ocean, or terrestrial) accumulate and persist in the subsurface ocean for decades to centuries. The simulated present-day atmosphere is enriched by a factor of 2.6 relative to 1840 levels, consistent with sediment archives, and by a factor of 7.5 relative to natural levels (2000 BC). Legacy anthropogenic Hg re-emitted from surface reservoirs accounts for 60% of present-day atmospheric deposition, compared to 27% from primary anthropogenic emissions, and 13% from natural sources. We find that only 17% of the present-day Hg in the surface ocean is natural and that half of its anthropogenic enrichment originates from pre-1950 emissions. Although Asia is presently the dominant contributor to primary anthropogenic emissions, only 17% of the surface ocean reservoir is of Asian anthropogenic origin, as compared to 30% of North American and European origin. The accumulated burden of legacy anthropogenic Hg means that future deposition will increase even if primary anthropogenic emissions are held constant. Aggressive global Hg emission reductions will be necessary just to maintain oceanic Hg concentrations at present levels.

/pdf/legacy-impacts-of-all-time-anthropogenic-emissions-on-the-15o0b8yux0.pdf

Legacy impacts of all‐time anthropogenic emissions on the global mercury cycle

We develop a mechanistic global model of soil mercury storage and emissions that tiesthe lifetime of mercury in soils to the lifetime of the organic carbon pools it is associatedwith We explore the implications of considering terrestrial mercury cycling in theframeworkofsoilcarboncyclingandsuggestpossibleavenuesoffutureresearchtotestourassumptions and constrain this type of model In our simulation, input of mercury to soil isby atmospheric deposition, in part through leaf uptake and subsequent litter fall, and ismoderated by surface photoreduction and revolatilization Once bound to organic carbon,mercury is transferred along a succession of short‐lived to long‐lived carbon pools and isultimately reemitted by respiration of these pools We examine the legacy of anthropogenicinfluence on global mercury storage and emissions and estimate that storage of mercury inorganic soils has increased by ∼20% since preindustrial times, while soil emissions haveincreased by a factor of 3 (2900 Mg yr

https://agupubs.onlinelibrary.wiley.com/doi/epdf/10.1029/2009JG001124

Anthropogenic impacts on global storage and emissions of mercury from terrestrial soils: Insights from a new global model

The soil sink of molecular hydrogen is the largest and most uncertain term in the global atmospheric H_2 budget. Lack of information about the mechanisms regulating this sink limits our ability to predict how atmospheric H_2 may respond to future changes in climate or anthropogenic emissions. Here we present the results from a series of laboratory experiments designed to systematically evaluate and describe the temperature and soil moisture dependence of H_2 uptake by soils from boreal forest and desert ecosystems. We observed substantial H2 uptake between −4°C and 0°C, a broad temperature optimum between 20°C and 30°C, a soil moisture optimum at approximately 20% saturation, and inhibition of uptake at both low and high soil moisture. A sigmoidal function described the temperature response of H_2 uptake by soils between −15°C and 40°C. Based on our results, we present a framework for a model of the soil H_2 sink.

/pdf/temperature-and-moisture-dependence-of-soil-h2-uptake-4c0et5a70t.pdf

Temperature and moisture dependence of soil H2 uptake measured in the laboratory

The mechanism and environmental controls on soil hydrogen (H_2) uptake are not well understood but are essential for understanding the atmospheric H_2 budget. Field observations of soil H_2 uptake are limited, and here we present the results from a series of measurements in forest, desert, and marsh ecosystems in southern California. We measured soil H_2 fluxes using flux chambers from September 2004 to July 2005. Mean H2 flux rates and standard deviations were −7.9 + −4.2, −7.6 + −5.3 and −7.5 + −3.4 nmol m^(−2) s^(−1) for the forest, desert, and marsh, respectively (corresponding to deposition velocities of 0.063 + −0.029, 0.051 + −0.036, 0.035 + −0.013 cm s^(−1)). Soil profile measurements showed that H_2 mixing ratios were between 3% and 51% of atmospheric levels at 10 cm and that the penetration of H_2 into deeper soil layers increased with soil drying. Soil removal experiments in the forest demonstrated that the litter layer did not actively consume H_2, the removal of this layer increased uptake by deeper soil layers, and the exposure of subsurface soil layers to ambient atmospheric H_2 levels substantially increased their rate of uptake. Similar soil removal experiments at the desert site showed that extremely dry surface soils did not consume H2 and that fluxes at the surface increased when these inactive layers were removed. We present a model of soil H_2 fluxes and show that the diffusivity of soils, along with the vertical distribution of layers that actively consume H_2 regulate surface fluxes. We found that soil organic matter, CO_2 fluxes, and ecosystem type were not strong controllers of H_2 uptake. Our experiments highlight H_2 diffusion into soils as an important limit on fluxes and that minimum moisture level is needed to initiate microbial uptake.

/pdf/molecular-hydrogen-uptake-by-soils-in-forest-desert-and-5808kbac6f.pdf

Nicole V. Smith-Downey

Papers

Anthropogenic impacts on global storage and emissions of mercury from terrestrial soils: Insights from a new global model

Temperature and moisture dependence of soil H2 uptake measured in the laboratory

Molecular hydrogen uptake by soils in forest, desert, and marsh ecosystems in California