Use of atmospheric concentrations and passive samplers to assess surface-atmosphere exchange of gaseous mercury in forests.

Direct measurements of gaseous elemental mercury (GEM) exchanges over global ecosystems are challenging and require extensive and costly measurement systems. Here, we explore the use of atmospheric GEM concentration variability and passive samplers to assess underlying ecosystem GEM exchanges at two rural temperate forests in the northeastern United States. We find strong temporal alignments between atmospheric GEM concentration declines and ecosystem GEM deposition in spring at both forests, which followed patterns of CO2 and suggests that ambient air GEM concentration monitoring provides a proxy measurement to assess forest GEM sinks. In fall, we observe GEM concentration increases and reversal of GEM fluxes to emissions, but with poor temporal alignments. Diel GEM concentration variability did not correspond to diel patterns of ecosystem GEM fluxes, which is driven by boundary layer dynamics with different atmospheric mixing depths during day- and nighttime. Passive samplers (PASs) deployed to measure vertical GEM gradients across six heights throughout one of the forest canopies showed excellent agreements with active measurements in detecting seasonal concentration patterns at all deployment heights. We find frequent qualitative agreement between the direction of active and PAS derived concentration gradients, but small concentration differences over small (1.3 and 4.9 m) distances prevent a quantitative comparison of methods. Furthermore, time-averaged GEM concentration gradient measurements are always biased towards stable nighttime periods, while ecosystem GEM fluxes are dominated by daytime exchanges, which results in the inability of integrated measurements such as PAS to correctly quantify forest GEM exchanges. We conclude that concentration measurements both via active and passive sampling can serve as proxies to assess underlying ecosystem GEM sinks and sources, but that the use of passive samplers to quantify GEM exchange via gradient measurements is limited due their strong nighttime biases.

Comparing ecosystem gaseous elemental mercury fluxes over a deciduous and coniferous forest.

Sources of neurotoxic mercury in forests are dominated by atmospheric gaseous elemental mercury (GEM) deposition, but a dearth of direct GEM exchange measurements causes major uncertainties about processes that determine GEM sinks. Here we present three years of forest-level GEM deposition measurements in a coniferous forest and a deciduous forest in northeastern USA, along with flux partitioning into canopy and forest floor contributions. Annual GEM deposition is 13.4 ± 0.80 µg m-2 (coniferous forest) and 25.1 ± 2.4 µg m-2 (deciduous forest) dominating mercury inputs (62 and 76% of total deposition). GEM uptake dominates in daytime during active vegetation periods and correlates with CO2 assimilation, attributable to plant stomatal uptake of mercury. Non-stomatal GEM deposition occurs in the coniferous canopy during nights and to the forest floor in the deciduous forest and accounts for 24 and 39% of GEM deposition, respectively. Our study shows that GEM deposition includes various pathways and is highly ecosystem-specific, which complicates global constraints of terrestrial GEM sinks.

Inorganic and methylated mercury dynamics in estuarine water of a salt marsh in Massachusetts, USA.

Salt marsh estuaries serve as sources and sinks for nutrients and elements to and from estuarine water, which enhances and alleviates watershed fluxes to the coastal ocean. We assessed sources and sinks of mercury in the intertidal Plum Island Sound estuary in Massachusetts, the largest salt marsh estuary of New England, using 25-km spatial water sampling transects. Across all seasons, dissolved (FHg) and total (THg) mercury concentrations in estuarine water were highest and strongly enhanced in upper marshes (1.31 ± 0.20 ng L-1 and 6.56 ± 3.70 ng L-1, respectively), compared to riverine Hg concentrations (0.86 ± 0.17 ng L-1 and 0.88 ± 0.34 ng L-1, respectively). Mercury concentrations declined from upper to lower marshes and were lowest in ocean water (0.38 ± 0.10 ng L-1 and 0.56 ± 0.25 ng L-1, respectively). Conservative mixing models using river and ocean water as endmembers indicated that internal estuarine Hg sources strongly enhanced estuarine water Hg concentrations. For FHg, internal estuarine Hg contributions were estimated at 26 g yr-1 which enhanced Hg loads from riverine sources to the ocean by 44%. For THg, internal sources amounted to 251 g yr-1 and exceeded riverine sources six-fold. Proposed sources for internal estuarine mercury contributions include atmospheric deposition to the large estuarine surface area and sediment re-mobilization, although sediment Hg concentrations were low (average 23 ± 2 µg kg-1) typical of uncontaminated sediments. Soil mercury concentrations under vegetation, however, were ten times higher (average 200 ± 225 µg kg-1) than in intertidal sediments suggesting that high soil Hg accumulation might drive lateral export of Hg to the ocean. Spatial transects of methylated Hg (MeHg) showed no concentration enhancements in estuarine water and no indication of internal MeHg sources or formation. Initial mass balance considerations suggest that atmospheric deposition may either be in similar magnitude, or possibly exceed lateral tidal export which would be consistent with strong Hg accumulation observed in salt marsh soils sequestering Hg from current and past atmospheric deposition.

Atmospheric mercury sources in a coastal-urban environment: a case study in Boston, Massachusetts, USA.

Mercury (Hg) is an environmental toxicant dangerous to human health and the environment. Its anthropogenic emissions are regulated by global, regional, and local policies. Here, we investigate Hg sources in the coastal city of Boston, the third largest metropolitan area in the Northeastern United States. With a median of 1.37 ng m-3, atmospheric Hg concentrations measured from August 2017 to April 2019 were at the low end of the range reported in the Northern Hemisphere and in the range reported at North American rural sites. Despite relatively low ambient Hg concentrations, we estimate anthropogenic emissions to be 3-7 times higher than in current emission inventories using a measurement-model framework, suggesting an underestimation of small point and/or nonpoint emissions. We also test the hypothesis that a legacy Hg source from the ocean contributes to atmospheric Hg concentrations in the study area; legacy emissions (recycling of previously deposited Hg) account for ∼60% of Hg emitted annually worldwide (and much of this recycling takes place through the oceans). We find that elevated concentrations observed during easterly oceanic winds can be fully explained by low wind speeds and recirculating air allowing for accumulation of land-based emissions. This study suggests that the influence of nonpoint land-based emissions may be comparable in size to point sources in some regions and highlights the benefits of further top-down studies in other areas.

Global Mercury Assimilation by Vegetation.

Assimilation of mercury (Hg) by vegetation represents one of the largest global environmental Hg mass fluxes. We estimate Hg assimilation by vegetation globally via a bottom-up scaling approach using tissue Hg concentrations synthesized from a comprehensive database multiplied by respective annual biomass production (NPP). As global annual NPP is close to annual vegetation die-off, Hg mass associated with global NPP approximates the transfer of Hg from plants to soils, which represents an estimate of vegetation-mediated atmospheric deposition. Annual vegetation assimilation of Hg from combined atmospheric and soil uptake is estimated at 3062 ± 607 Mg yr-1, which is composed of 2491 ± 551 Mg yr-1 from aboveground tissue uptake and 571 ± 253 Mg yr-1 from root uptake. Assimilation of atmospheric Hg amounts to 2422 ± 483 Mg yr-1 when considering aboveground tissues only. Atmospheric assimilation increases to 2705 ± 504 Mg yr-1 when considering that root Hg may be partially derived from prior foliar uptake and transported internally to roots. Estimated atmospheric Hg assimilation by vegetation is 54-137% larger than the current model and litterfall estimates, largely because of the inclusion of lichens, mosses, and woody tissues in deposition and all global biomes. Belowground, about 50% of root Hg was taken up from soils with currently unknown ecological and biogeochemical consequences.

Previously unaccounted atmospheric mercury deposition in a midlatitude deciduous forest.

Mercury is toxic to wildlife and humans, and forests are thought to be a globally important sink for gaseous elemental mercury (GEM) deposition from the atmosphere. Yet there are currently no annual GEM deposition measurements over rural forests. Here we present measurements of ecosystem-atmosphere GEM exchange using tower-based micrometeorological methods in a midlatitude hardwood forest. We measured an annual GEM deposition of 25.1 µg ⋅ m-2 (95% CI: 23.2 to 26.7 1 µg ⋅ m-2), which is five times larger than wet deposition of mercury from the atmosphere. Our observed annual GEM deposition accounts for 76% of total atmospheric mercury deposition and also is three times greater than litterfall mercury deposition, which has previously been used as a proxy measure for GEM deposition in forests. Plant GEM uptake is the dominant driver for ecosystem GEM deposition based on seasonal and diel dynamics that show the forest GEM sink to be largest during active vegetation growing periods and middays, analogous to photosynthetic carbon dioxide assimilation. Soils and litter on the forest floor are additional GEM sinks throughout the year. Our study suggests that mercury loading to this forest was underestimated by a factor of about two and that global forests may constitute a much larger global GEM sink than currently proposed. The larger than anticipated forest GEM sink may explain the high mercury loads observed in soils across rural forests, which impair water quality and aquatic biota via watershed Hg export.

Chemical speciation of trace metals in atmospheric deposition and impacts on soil geochemistry and vegetable bioaccumulation near a large copper smelter in China.

Atmospheric deposition is an important source of trace metals to surface environments, but knowledge about plant bioavailability of recently deposited metals and their fate in the soil-plant system is limited. We performed a fully factorial soil and atmosphere exposure experiment with three vegetables (radish, lettuce, and soybean). Treatments included soil profiles collected from three sites located along a strong gradient of atmospheric deposition with each soil type deployed across the three sites for one year, which allowed to effectively distinguish impacts of recently deposited metals (<1 year) from longer-term trace metal exposures in soils. Results showed that recently deposited copper (Cu), cadmium (Cd), and lead (Pb) accounted for 0.5-15.2% of total soil Cu, Cd, and Pb pools at the site most heavily impacted by atmospheric deposition, while recent deposition contributed 15-76% of Cu, Cd, and Pb concentrations in edible parts of vegetables. In addition, soil geochemical extractions showed that bioavailable fractions of trace metals from recent deposition (52-73%) were higher compared to metals previously present in soils (7-42%). These findings highlight a preferential uptake and high rates of bioaccumulation of deposited metals in vegetables and suggest a high potential of environmental risks of food pollution under high atmospheric metal deposition.

Vegetation Mediated Mercury Flux and Atmospheric Mercury in the Alpine Permafrost Region of the Central Tibetan Plateau.

Measurements of land-air mercury (Hg) exchanges over vegetated surfaces are needed to further constrain Hg fluxes over vegetated terrestrial surfaces. Yet, knowledge of land-air Hg dynamics in alpine grasslands remains poor. Hg fluxes over an alpine meadow were measured throughout a full vegetation period in the central Tibetan Plateau (TP). This TP grassland served as a small source of atmospheric total gaseous Hg (TGM) during vegetation period (0.92 µg m-2). Hg fluxes decreased logarithmically during plant growing season, resulting from the influence of vegetation by light shading and plant Hg uptake, although the latter might be minor due to low biomass at this site. Temporal patterns of TGM indicated the importance of land-air dynamics in regulating TGM levels. During the plant emergence, diel pattern of TGM covaried with Hg emission fluxes resulting in lower concentrations at night and higher concentrations in afternoon. During all other vegetation stages, TGM showed minima before dawn and "morning peak" shortly after sunrise, in conjunction with corresponding Hg fluxes showing sink before dawn and source after sunrise. Moreover, TGM concentrations showed a decreasing trend with plant growing, further indicating the role of vegetation in driving seasonal TGM variations by regulating land-air Hg dynamics.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol-1; 4.2 × 108 atoms per cm-3) and were up to 3-10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

Mercury emission from industrially contaminated soils in relation to chemical, microbial, and meteorological factors.

The Minamata Convention entered into force in 2017 with the aim to phase-out the use of mercury (Hg) in manufacturing processes such as the chlor-alkali or vinyl chloride monomer production. However, past industrial use of Hg had already resulted in extensive soil pollution, which poses a potential environmental threat. We investigated the emission of gaseous elemental mercury (Hg0) from Hg polluted soils in settlement areas in the canton of Valais, Switzerland, and its impact on local air Hg concentrations. Most soil Hg was found as soil matrix-bound divalent Hg (HgII). Elemental mercury (Hg0) was undetectable in soils, yet we observed substantial Hg0 emission (20-1392 ng m-2 h-1) from 27 soil plots contaminated with Hg (0.2-390 mg Hg kg-1). The emissions of Hg0 were calculated for 1274 parcels covering an area of 8.6 km2 of which 12% exceeded the Swiss soil remediation threshold of 2 mg Hg kg-1. The annual Hg0 emission from this area was approximately 6 kg a-1, which is almost 1% of the total atmospheric Hg emissions in Switzerland based on emission inventory estimates. Our results show a higher abundance of Hg resistance genes (merA) in soil microbial communities with increasing soil Hg concentrations, indicating that biotic reduction of HgII is likely an important pathway to form volatile Hg0 in these soils. The total soil Hg pool in the top 20 cm of the investigated area was 4288 kg; hence, if not remediated, these contaminated soils remain a long-term source of atmospheric Hg, which is prone to long-range atmospheric transport.

Mercury in tundra vegetation of Alaska: Spatial and temporal dynamics and stable isotope patterns.

Vegetation uptake of atmospheric mercury (Hg) is an important mechanism enhancing atmospheric Hg deposition via litterfall and senescence. We here report Hg concentrations and pool sizes of different plant functional groups and plant species across nine tundra sites in northern Alaska. Significant spatial differences were observed in bulk vegetation Hg concentrations at Toolik Field station (52 ±â€¯9 µg kg-1), Eight Mile Lake Observatory (40 ±â€¯0.2 µg kg-1), and seven sites along a transect from Toolik Field station to the Arctic coast (36 ±â€¯9 µg kg-1). Hg concentrations in non-vascular vegetation including feather and peat moss (58 ±â€¯6 µg kg-1 and 34 ±â€¯2 µg kg-1, respectively) and brown and white lichen (41 ±â€¯2 µg kg-1 and 34 ±â€¯2 µg kg-1, respectively), were three to six times those of vascular plant tissues (8 ±â€¯1 µg kg-1 in dwarf birch leaves and 9 ±â€¯1 µg kg-1 in tussock grass). A high representation of nonvascular vegetation in aboveground biomass resulted in substantial Hg mass contained in tundra aboveground vegetation (29 µg m-2), which fell within the range of foliar Hg mass estimated for forests in the United States (15 to 45 µg m-2) in spite of much shorter growing seasons. Hg stable isotope signatures of different plant species showed that atmospheric Hg(0) was the dominant source of Hg to tundra vegetation. Mass-dependent isotope signatures (δ202Hg) in vegetation relative to atmospheric Hg(0) showed pronounced shifts towards lower values, consistent with previously reported isotopic fractionation during foliar uptake of Hg(0). Mass-independent isotope signatures (Δ199Hg) of lichen were more positive relative to atmospheric Hg(0), indicating either photochemical reduction of Hg(II) or contributions of inorganic Hg(II) from atmospheric deposition and/or dust. Δ199Hg and Δ200Hg values in vascular plant species were similar to atmospheric Hg(0) suggesting that overall photochemical reduction and subsequent re-emission was relatively insignificant in these tundra ecosystems, in agreement with previous Hg(0) ecosystem flux measurements.

A Critical Time for Mercury Science to Inform Global Policy.

Mercury is a global pollutant released into the biosphere by varied human activities including coal combustion, mining, artisanal gold mining, cement production, and chemical production. Once released to air, land and water, the addition of carbon atoms to mercury by bacteria results in the production of methylmercury, the toxic form that bioaccumulates in aquatic and terrestrial food chains resulting in elevated exposure to humans and wildlife. Global recognition of the mercury contamination problem has resulted in the Minamata Convention on Mercury, which came into force in 2017. The treaty aims to protect human health and the environment from human-generated releases of mercury curtailing its movement and transformations in the biosphere. Coincident with the treaty's coming into force, the 13th International Conference of Mercury as a Global Pollutant (ICMGP-13) was held in Providence, Rhode Island USA. At ICMGP-13, cutting edge research was summarized and presented to address questions relating to global and regional sources and cycling of mercury, how that mercury is methylated, the effects of mercury exposure on humans and wildlife, and the science needed for successful implementation of the Minamata Convention. Human activities have the potential to enhance mercury methylation by remobilizing previously released mercury, and increasing methylation efficiency. This synthesis concluded that many of the most important factors influencing the fate and effects of mercury and its more toxic form, methylmercury, stem from environmental changes that are much broader in scope than mercury releases alone. Alterations of mercury cycling, methylmercury bioavailability and trophic transfer due to climate and land use changes remain critical uncertainties in effective implementation of the Minamata Convention. In the face of these uncertainties, important policy and management actions are needed over the short-term to support the control of mercury releases to land, water and air. These include adequate monitoring and communication on risk from exposure to various forms of inorganic mercury as well as methylmercury from fish and rice consumption. Successful management of global and local mercury pollution will require integration of mercury research and policy in a changing world.

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

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.

Tundra uptake of atmospheric elemental mercury drives Arctic mercury pollution.

Anthropogenic activities have led to large-scale mercury (Hg) pollution in the Arctic. It has been suggested that sea-salt-induced chemical cycling of Hg (through 'atmospheric mercury depletion events', or AMDEs) and wet deposition via precipitation are sources of Hg to the Arctic in its oxidized form (Hg(ii)). However, there is little evidence for the occurrence of AMDEs outside of coastal regions, and their importance to net Hg deposition has been questioned. Furthermore, wet-deposition measurements in the Arctic showed some of the lowest levels of Hg deposition via precipitation worldwide, raising questions as to the sources of high Arctic Hg loading. Here we present a comprehensive Hg-deposition mass-balance study, and show that most of the Hg (about 70%) in the interior Arctic tundra is derived from gaseous elemental Hg (Hg(0)) deposition, with only minor contributions from the deposition of Hg(ii) via precipitation or AMDEs. We find that deposition of Hg(0)-the form ubiquitously present in the global atmosphere-occurs throughout the year, and that it is enhanced in summer through the uptake of Hg(0) by vegetation. Tundra uptake of gaseous Hg(0) leads to high soil Hg concentrations, with Hg masses greatly exceeding the levels found in temperate soils. Our concurrent Hg stable isotope measurements in the atmosphere, snowpack, vegetation and soils support our finding that Hg(0) dominates as a source to the tundra. Hg concentration and stable isotope data from an inland-to-coastal transect show high soil Hg concentrations consistently derived from Hg(0), suggesting that the Arctic tundra might be a globally important Hg sink. We suggest that the high tundra soil Hg concentrations might also explain why Arctic rivers annually transport large amounts of Hg to the Arctic Ocean.

Inversion Approach to Validate Mercury Emissions Based on Background Air Monitoring at the High Altitude Research Station Jungfraujoch (3580 m).

The reduction of emissions of mercury is a declared aim of the Minamata Convention, a UN treaty designed to protect human health and the environment from adverse effects of mercury. To assess the effectiveness of the convention in the future, better constraints about the current mercury emissions is a premise. In our study, we applied a top-down approach to quantify mercury emissions on the basis of atmospheric mercury measurements conducted at the remote high altitude monitoring station Jungfraujoch, Switzerland. We established the source-receptor relationships and by the means of atmospheric inversion we were able to quantify spatially resolved European emissions of 89 ± 14 t/a for elemental mercury. Our European emission estimate is 17% higher than the bottom-up emission inventory, which is within stated uncertainties. However, some regions with unexpectedly high emissions were identified. Stationary combustion, in particular in coal-fired power plants, is found to be the main responsible sector for increased emission estimates. Our top-down approach, based on measurements, provides an independent constraint on mercury emissions, helps to improve and refine reported emission inventories, and can serve for continued assessment of future changes in emissions independent from bottom-up inventories.

Mercury in western North America: A synthesis of environmental contamination, fluxes, bioaccumulation, and risk to fish and wildlife.

Western North America is a region defined by extreme gradients in geomorphology and climate, which support a diverse array of ecological communities and natural resources. The region also has extreme gradients in mercury (Hg) contamination due to a broad distribution of inorganic Hg sources. These diverse Hg sources and a varied landscape create a unique and complex mosaic of ecological risk from Hg impairment associated with differential methylmercury (MeHg) production and bioaccumulation. Understanding the landscape-scale variation in the magnitude and relative importance of processes associated with Hg transport, methylation, and MeHg bioaccumulation requires a multidisciplinary synthesis that transcends small-scale variability. The Western North America Mercury Synthesis compiled, analyzed, and interpreted spatial and temporal patterns and drivers of Hg and MeHg in air, soil, vegetation, sediments, fish, and wildlife across western North America. This collaboration evaluated the potential risk from Hg to fish, and wildlife health, human exposure, and examined resource management activities that influenced the risk of Hg contamination. This paper integrates the key information presented across the individual papers that comprise the synthesis. The compiled information indicates that Hg contamination is widespread, but heterogeneous, across western North America. The storage and transport of inorganic Hg across landscape gradients are largely regulated by climate and land-cover factors such as plant productivity and precipitation. Importantly, there was a striking lack of concordance between pools and sources of inorganic Hg, and MeHg in aquatic food webs. Additionally, water management had a widespread influence on MeHg bioaccumulation in aquatic ecosystems, whereas mining impacts where relatively localized. These results highlight the decoupling of inorganic Hg sources with MeHg production and bioaccumulation. Together the findings indicate that developing efforts to control MeHg production in the West may be particularly beneficial for reducing food web exposure instead of efforts to simply control inorganic Hg sources.

Estimating mercury emissions resulting from wildfire in forests of the Western United States.

Understanding the emissions of mercury (Hg) from wildfires is important for quantifying the global atmospheric Hg sources. Emissions of Hg from soils resulting from wildfires in the Western United States was estimated for the 2000 to 2013 period, and the potential emission of Hg from forest soils was assessed as a function of forest type and soil-heating. Wildfire released an annual average of 3100±1900kg-Hgy(-1) for the years spanning 2000-2013 in the 11 states within the study area. This estimate is nearly 5-fold lower than previous estimates for the study region. Lower emission estimates are attributed to an inclusion of fire severity within burn perimeters. Within reported wildfire perimeters, the average distribution of low, moderate, and high severity burns was 52, 29, and 19% of the total area, respectively. Review of literature data suggests that that low severity burning does not result in soil heating, moderate severity fire results in shallow soil heating, and high severity fire results in relatively deep soil heating (<5cm). Using this approach, emission factors for high severity burns ranged from 58 to 640µg-Hgkg-fuel(-1). In contrast, low severity burns have emission factors that are estimated to be only 18-34µg-Hgkg-fuel(-1). In this estimate, wildfire is predicted to release 1-30gHgha(-1) from Western United States forest soils while above ground fuels are projected to contribute an additional 0.9 to 7.8gHgha(-1). Land cover types with low biomass (desert scrub) are projected to release less than 1gHgha(-1). Following soil sources, fuel source contributions to total Hg emissions generally followed the order of duff>wood>foliage>litter>branches.

A synthesis of terrestrial mercury in the western United States: Spatial distribution defined by land cover and plant productivity.

A synthesis of published vegetation mercury (Hg) data across 11 contiguous states in the western United States showed that aboveground biomass concentrations followed the order: leaves (26µgkg(-1))~branches (26µgkg(-1))>bark (16µgkg(-1))>bole wood (1µgkg(-1)). No spatial trends of Hg in aboveground biomass distribution were detected, which likely is due to very sparse data coverage and different sampling protocols. Vegetation data are largely lacking for important functional vegetation types such as shrubs, herbaceous species, and grasses. Soil concentrations collected from the published literature were high in the western United States, with 12% of observations exceeding 100µgkg(-1), reflecting a bias toward investigations in Hg-enriched sites. In contrast, soil Hg concentrations from a randomly distributed data set (1911 sampling points; Smith et al., 2013a) averaged 24µgkg(-1) (A-horizon) and 22µgkg(-1) (C-horizon), and only 2.6% of data exceeded 100µgkg(-1). Soil Hg concentrations significantly differed among land covers, following the order: forested upland>planted/cultivated>herbaceous upland/shrubland>barren soils. Concentrations in forests were on average 2.5 times higher than in barren locations. Principal component analyses showed that soil Hg concentrations were not or weakly related to modeled dry and wet Hg deposition and proximity to mining, geothermal areas, and coal-fired power plants. Soil Hg distribution also was not closely related to other trace metals, but strongly associated with organic carbon, precipitation, canopy greenness, and foliar Hg pools of overlying vegetation. These patterns indicate that soil Hg concentrations are related to atmospheric deposition and reflect an overwhelming influence of plant productivity - driven by water availability - with productive landscapes showing high soil Hg accumulation and unproductive barren soils and shrublands showing low soil Hg values. Large expanses of low-productivity, arid ecosystems across the western U.S. result in some of the lowest soil Hg concentrations observed worldwide.

New Constraints on Terrestrial Surface-Atmosphere Fluxes of Gaseous Elemental Mercury Using a Global Database.

Despite 30 years of study, gaseous elemental mercury (Hg(0)) exchange magnitude and controls between terrestrial surfaces and the atmosphere still remain uncertain. We compiled data from 132 studies, including 1290 reported fluxes from more than 200,000 individual measurements, into a database to statistically examine flux magnitudes and controls. We found that fluxes were unevenly distributed, both spatially and temporally, with strong biases toward Hg-enriched sites, daytime and summertime measurements. Fluxes at Hg-enriched sites were positively correlated with substrate concentrations, but this was absent at background sites. Median fluxes over litter- and snow-covered soils were lower than over bare soils, and chamber measurements showed higher emission compared to micrometeorological measurements. Due to low spatial extent, estimated emissions from Hg-enriched areas (217 Mg·a(-1)) were lower than previous estimates. Globally, areas with enhanced atmospheric Hg(0) levels (particularly East Asia) showed an emerging importance of Hg(0) emissions accounting for half of the total global emissions estimated at 607 Mg·a(-1), although with a large uncertainty range (-513 to 1353 Mg·a(-1) [range of 37.5th and 62.5th percentiles]). The largest uncertainties in Hg(0) fluxes stem from forests (-513 to 1353 Mg·a(-1) [range of 37.5th and 62.5th percentiles]), largely driven by a shortage of whole-ecosystem fluxes and uncertain contributions of leaf-atmosphere exchanges, questioning to what degree ecosystems are net sinks or sources of atmospheric Hg(0).