Global mercury concentrations in biota: their use as a basis for a global biomonitoring framework.

An important provision of the Minamata Convention on Mercury is to monitor and evaluate the effectiveness of the adopted measures and its implementation. Here, we describe for the first time currently available biotic mercury (Hg) data on a global scale to improve the understanding of global efforts to reduce the impact of Hg pollution on people and the environment. Data from the peer-reviewed literature were compiled in the Global Biotic Mercury Synthesis (GBMS) database (>550,000 data points). These data provide a foundation for establishing a biomonitoring framework needed to track Hg concentrations in biota globally. We describe Hg exposure in the taxa identified by the Minamata Convention: fish, sea turtles, birds, and marine mammals. Based on the GBMS database, Hg concentrations are presented at relevant geographic scales for continents and oceanic basins. We identify some effective regional templates for monitoring methylmercury (MeHg) availability in the environment, but overall illustrate that there is a general lack of regional biomonitoring initiatives around the world, especially in Africa, Australia, Indo-Pacific, Middle East, and South Atlantic and Pacific Oceans. Temporal trend data for Hg in biota are generally limited. Ecologically sensitive sites (where biota have above average MeHg tissue concentrations) have been identified throughout the world. Efforts to model and quantify ecosystem sensitivity locally, regionally, and globally could help establish effective and efficient biomonitoring programs. We present a framework for a global Hg biomonitoring network that includes a three-step continental and oceanic approach to integrate existing biomonitoring efforts and prioritize filling regional data gaps linked with key Hg sources. We describe a standardized approach that builds on an evidence-based evaluation to assess the Minamata Convention's progress to reduce the impact of global Hg pollution on people and the environment.

Variation in habitat use and its consequences for mercury exposure in two Eastern Ontario bat species, Myotis lucifugus and Eptesicus fuscus.

The St. Lawrence River in Eastern Ontario, Canada, has been a designated an area of concern due to past industrial contamination of sediment in some areas and transport of mercury from tributaries. Previous research using bats as sentinel species identified elevated concentrations of total mercury (THg) in fur of local bats and species-specific variation between little brown bats (Myotis lucifugus) and big brown bats (Eptesicus fuscus). Here, we investigated the mercury exposure pathways for these two species by testing the hypothesis that diet variation, particularly the reliance on aquatic over terrestrial insects, is a determinant of local bat mercury concentrations. We analyzed THg concentration and stable isotope ratios of δ15N and δ13C in fur of little and big brown bats, and in aquatic and terrestrial insects. Big brown bats, especially males, accumulated significantly higher THg concentrations in their fur compared to little brown bats. However, this difference was not related to diet because big brown bats consumed terrestrial insects, which were lower in mercury than aquatic insects, the primary prey for little brown bats. We also evaluated whether fur THg concentrations translate into molecular changes in tissues linked to (methyl)mercury toxicity by quantifying tissue changes in global DNA methylation and mitochondrial DNA abundance. No significant changes in DNA molecular markers were observed in relation to fur THg concentration, suggesting mercury exposure to local bats did not impact molecular level changes at the DNA level. Higher mercury in bats was not associated with local aquatic contamination or genotoxicity in this study area.

Vanadium Stable Isotopes in Biota of Terrestrial and Aquatic Food Chains.

Vanadium, a potentially toxic metal, is enriched in the environment from anthropogenic releases, particularly during fossil fuel production and use and steel manufacturing. Metal stable isotopes are sophisticated tools to trace pollution; however, only recent analytical advances have allowed for the accurate and precise measurement of vanadium isotope ratios (δ51V). To examine its potential as a tracer in terrestrial and aquatic ecosystems, δ51V was measured in soil, plant, lichen, marten, and lake sediment from sites near vanadium emissions at oil sands mines (Alberta, Canada) and in the sediment and biota (algae, zooplankton, fish) from a remote subarctic lake (Northwest Territories, Canada). Samples from Alberta had distinct δ51V values with marten liver the lowest (-1.7 ± 0.3‰), followed by lichen (-0.9 ± 0.1‰), soil (-0.7 ± 0.1‰), sediment (-0.5 ± 0.2‰), and plant root (-0.3 ± 0.2‰). Average values were lower than Alberta bitumen and petroleum coke (-0.1 ± 0.1‰). Plant roots had systematically higher δ51V than the soil from which they grew (Δ51Vplant-soil = 0.4 ± 0.1‰), while δ51V of lichen and aquatic biota were lower (0.1-0.3‰) than likely crustal sources. These δ51V measurements in terrestrial and aquatic biota demonstrate promise for tracer applications, although further study of its biological fractionation is needed.

Environmental Drivers of Rare Earth Element Bioaccumulation in Freshwater Zooplankton.

Human activities have resulted in significant release of rare earth elements (REEs) into the environment. However, the pathways of REEs from waters and soils into freshwater food webs remain poorly understood. Recent studies suggest that aquatic invertebrates may be good biomonitors for REEs, yet there is little information on factors that control REE bioaccumulation in these organisms. Our goal was to study the environmental drivers of REE levels in zooplankton, a key component in plankton food webs, across lakes from geographic areas with different bedrock geology. From 2011 to 2014, bulk zooplankton samples were collected for REE analysis from 39 lakes in eastern Canada. We observed a more than 200 fold variation in surface water REE concentrations and a 10-fold variation in sediment REE concentrations. These concentration gradients were associated with a range of more than an order of magnitude in zooplankton REE concentrations (∑REEY 3.2-210 nmol g-1). We found higher REE bioaccumulation in zooplankton from lakes with lower pH and higher REE to dissolved organic carbon ratios. Bioaccumulation was also strongly linked to the free ion concentrations of REEs (REE3+) in surface waters. Our study suggests that zooplankton REE bioaccumulation is an excellent predictor of bioavailable REEs in freshwaters.

Ratio of Methylmercury to Dissolved Organic Carbon in Water Explains Methylmercury Bioaccumulation Across a Latitudinal Gradient from North-Temperate to Arctic Lakes.

We investigated monomethylmercury (MMHg) bioaccumulation in lakes across a 30° latitudinal gradient in eastern Canada to test the hypothesis that climate-related environmental conditions affect the sensitivity of Arctic lakes to atmospheric mercury contamination. Aquatic invertebrates (chironomid larvae, zooplankton) provided indicators of MMHg bioaccumulation near the base of benthic and planktonic food chains. In step with published data showing latitudinal declines in atmospheric mercury deposition in Canada, we observed lower total mercury concentrations in water and sediment of higher latitude lakes. Despite latitudinal declines of inorganic mercury exposure, MMHg bioaccumulation in aquatic invertebrates did not concomitantly decline. Arctic lakes with greater MMHg in aquatic invertebrates either had (1) higher water MMHg concentrations (reflecting ecosystem MMHg production) or (2) low water concentrations of MMHg, dissolved organic carbon (DOC), chlorophyll, and total nitrogen (reflecting lake sensitivity). The MMHg:DOC ratio of surface water was a strong predictor of lake sensitivity to mercury contamination. Bioaccumulation factors for biofilms and seston in Arctic lakes showed more efficient uptake of MMHg in low DOC systems. Environmental conditions associated with low biological production in Arctic lakes and their watersheds increased the sensitivity of lakes to MMHg.

High Methylmercury in Arctic and Subarctic Ponds is Related to Nutrient Levels in the Warming Eastern Canadian Arctic.

Permafrost thaw ponds are ubiquitous in the eastern Canadian Arctic, yet little information exists on their potential as sources of methylmercury (MeHg) to freshwaters. They are microbially active and conducive to methylation of inorganic mercury, and are also affected by Arctic warming. This multiyear study investigated thaw ponds in a discontinuous permafrost region in the Subarctic taiga (Kuujjuarapik-Whapmagoostui, QC) and a continuous permafrost region in the Arctic tundra (Bylot Island, NU). MeHg concentrations in thaw ponds were well above levels measured in most freshwater ecosystems in the Canadian Arctic (>0.1 ng L(-1)). On Bylot, ice-wedge trough ponds showed significantly higher MeHg (0.3-2.2 ng L(-1)) than polygonal ponds (0.1-0.3 ng L(-1)) or lakes (<0.1 ng L(-1)). High MeHg was measured in the bottom waters of Subarctic thaw ponds near Kuujjuarapik (0.1-3.1 ng L(-1)). High water MeHg concentrations in thaw ponds were strongly correlated with variables associated with high inputs of organic matter (DOC, a320, Fe), nutrients (TP, TN), and microbial activity (dissolved CO2 and CH4). Thawing permafrost due to Arctic warming will continue to release nutrients and organic carbon into these systems and increase ponding in some regions, likely stimulating higher water concentrations of MeHg. Greater hydrological connectivity from permafrost thawing may potentially increase transport of MeHg from thaw ponds to neighboring aquatic ecosystems.

Effects of experimental thermocline and oxycline deepening on methylmercury bioaccumulation in a Canadian shield lake.

Environmental disturbances like deforestation or climate change may influence lake thermal and oxic stratification, thereby modifying cycles of contaminants such as mercury (Hg). In a lake naturally separated into three basins, the thermocline and oxycline of an experimental basin were deepened by 4 and 3 m, respectively, to study the effect on the methylmercury (MeHg) accumulation. This treatment decreased hypolimnetic MeHg concentration by approximately 90%, zooplankton concentrations by 30 to 50%, and in some fish by 45%. A multiple linear regression indicated that oxycline depth significantly influenced hypolimnetic MeHg concentrations, with no significant effect of thermocline depth, anoxic water volume, interface area of oxic-anoxic water, and sediment area in contact with anoxic water. Fish MeHg decline varied, with a greater response by low oxygen-tolerant bullhead. Increased pelagic primary and secondary production likely caused zooplankton and fish MeHg decreases via algal and growth dilution. Environmental changes leading to oxycline deepening are therefore predicted to cause a decrease in MeHg bioaccumulation in similar Canadian Shield lakes. If associated ecosystem impacts related to the deepening treatment are deemed acceptable, then this experiment provides a potential remediation method for small lakes confronted with MeHg accumulation.

Environmental, geographic and trophic influences on methylmercury concentrations in macroinvertebrates from lakes and wetlands across Canada.

Macroinvertebrates are a key vector in the transfer of methylmercury (MeHg) to fish. However, the factors that affect MeHg concentrations and bioaccumulation in these organisms are not as well understood as for fish, and studies on a broad geographic scale are lacking. In this study, we gathered published and unpublished MeHg and carbon (δ(13)C) and nitrogen (δ(15)N) stable isotope data for freshwater macroinvertebrates from 119 lakes and wetlands across seven Canadian provinces, along with selected physical, chemical and biological characteristics of these systems. Overall, water pH was the most important determinant of MeHg concentrations in both predatory and non-predatory invertebrates [[Formula: see text] = 0.32, p < 0.001; multivariate canonical redundancy analysis (RDA)]. The location of lakes explained additional variation in invertebrate MeHg (partial R(2) = 0.08 and 0.06 for latitude and longitude, respectively; RDA), with higher concentrations in more easterly and southerly regions. Both invertebrate foraging behaviour and trophic position (indicated by functional feeding groups and δ(15)N values, respectively) also predicted MeHg concentrations in the organisms. Collectively, results indicate that in addition to their feeding ecology, invertebrates accumulate more MeHg in acidic systems where the supply of MeHg to the food web is typically high. MeHg concentrations in macroinvertebrates may also be influenced by larger-scale geographic differences in atmospheric mercury deposition among regions.

Watershed hydrology mediates the recovery of an arsenic impacted subarctic landscape.

A holistic understanding of the chemical recovery of lakes from arsenic (As) pollution requires consideration of within-lake biogeochemical cycling of As and processes occurring in the surrounding catchment. This study used a watershed mass balance approach, complemented by experimental sediment incubations, to assess the mobility and transport of As within a subarctic watershed (155 km2) impacted by more than 60 years of atmospheric mining emissions. The period of record spanned a transition from drought to high streamflow between September 2017 and September 2019, which yielded insights into the interacting effects of hydrology and within-lake biogeochemical cycling of As. Internal loading of As from contaminated lake sediments (25 - 46 kg As year-1) and contributions from terrestrial sources (16 - 56 kg As yr-1) continue to negatively impact lake water quality (19 - 144 µg As L-1), but the relative importance of these loads varies seasonally and inter-annually in response to changing hydrological conditions. Wet conditions resulted in greater transport of As from terrestrial reservoirs and upstream areas, shorter lake water retention time, and increased the downstream export of As. During dry periods, the lake was disconnected from the surrounding watershed resulting in limited terrestrial contributions and longer lake water residence time, which delayed recovery due to the greater relative influence of internal loading from contaminated sediments. This study highlights that changing hydroclimatic regimes will alter trajectories of chemical recovery for arsenic impacted lakes through the coupling of within-lake and watershed transport processes.

Contrasting trophic transfer patterns of cadmium and mercury in the Arctic marine food web of east Hudson Bay, Canada.

We investigated trophic transfer of cadmium (Cd) through an Arctic marine food web in Hudson Bay and compared it with mercury (Hg), a metal known to strongly biomagnify. We evaluated blue mussel, sea urchin, common eider, sculpin, Arctic cod, and ringed seal for the influence of dietary and biological variables on variation in Cd and Hg concentrations. Age and size influenced metal concentrations among individuals within a vertebrate species. Consumer carbon and sulfur isotope values were correlated with their Cd and Hg concentrations, indicating habitat-specific feeding influenced metal bioaccumulation. Trophic transfer patterns for Cd depended on the vertebrate tissue, with food web biodilution observed for the muscle but not the liver. Liver Cd concentrations were higher in ringed seal and some common eider relative to prey. In contrast, we observed mercury biomagnification for both tissues. Tissue- and species-specific physiology can explain discrepancies of Cd trophic transfer in this Arctic marine food web.

An investigation of enhanced mercury bioaccumulation in fish from offshore feeding.

We investigated the dietary pathways of mercury transfer in the food web of Morency Lake (Canada) to determine the influence of carbon source and habitat use on mercury bioaccumulation in fish. Whole-body concentrations of methylmercury (MeHg) were significantly different in four fish species (white sucker, brown bullhead, pumpkinseed and smallmouth bass) and increased with both trophic position and greater feeding on offshore (versus littoral) carbon. An examination of fish gut contents and the depth distribution of invertebrates in Morency Lake showed that smallmouth bass and brown bullhead were supplementing their littoral diet with the consumption of either opossum shrimp (Mysis diluviana) or profundal amphipods in offshore waters. The zooplanktivore Mysis had significantly higher MeHg concentrations than zooplankton and benthic invertebrates, and it was an elevated source of MeHg to smallmouth bass. In contrast, profundal amphipods consumed by brown bullhead did not have higher MeHg concentrations than littoral amphipods. Instead, partitioning of benthic invertebrate resources likely explains the greater MeHg bioaccumulation in brown bullhead, associated with offshore feeding of amphipods. White sucker and brown bullhead had a similar trophic position but white sucker consumed more chironomids, which had one-third the MeHg concentration of amphipods. Our findings suggest that offshore feeding in a lake can affect fish MeHg bioaccumulation via two different processes: (1) the consumption of MeHg-enriched pelagic prey, or (2) resource partitioning of benthic primary consumers with different MeHg concentrations. These observations on the mechanisms of habitat-specific bioaccumulation highlight the complexity of MeHg transfer through lake food webs.

Remobilization of legacy arsenic from sediment in a large subarctic waterbody impacted by gold mining.

Arsenic contamination from mining poses an environmental challenge due to the mobility of this redox-sensitive element. This study evaluated arsenic mobility in sediments of Yellowknife Bay (Canada), a large subarctic water body impacted by gold mining during the 20th century. Short-term measurements of arsenic flux from sediment, arsenic profiling of the water column and sediment porewater, and mass balance modelling were conducted to assess the importance of sediment as an arsenic source. Sediment arsenic fluxes were highly variable throughout Yellowknife Bay and ranged from - 65-1520 µg m-2 day-1. Elevated fluxes measured near the mine site were among the highest published for well-oxygenated lakes. Redox boundaries were typically 2-3 cm below the sediment surface as indicated by porewater profiles of iron, manganese, and arsenic, with arsenic maxima of 65-3220 µg L-1 predominately as arsenite. Sediment arsenic flux was positively related to its solid-phase concentration. Modelling indicated sediment was a principal source of arsenic to the water column. Adsorption and precipitation processes in the oxidizing environment of near-surface sediments did not effectively attenuate arsenic remobilized from contaminated sediments. Internal recycling of legacy arsenic between sediment and surface water will impede a return to background conditions in Yellowknife Bay for decades.

Diet and landscape characteristics drive spatial patterns of mercury accumulation in a high-latitude terrestrial carnivore.

Limited information exists on mercury concentrations and environmental drivers of mercury bioaccumulation in high latitude terrestrial carnivores. Spatial patterns of mercury concentrations in wolverine (Gulo gulo, n = 419) were assessed across a 1,600,000 km2 study area in relation to landscape, climate, diet and biological factors in Arctic and boreal biomes of western Canada. Hydrogen stable isotope ratios were measured in wolverine hair from a subset of 80 animals to assess the spatial scale for characterizing environmental conditions of their habitat. Habitat characteristics were determined using GIS methods and raster datasets at two scales, the collection location point and a 150 km radius buffer, which was selected based on results of a correlation analysis between hydrogen stable isotopes in precipitation and wolverine hair. Total mercury concentrations in wolverine muscle ranged >2 orders of magnitude from 0.01 to 5.72 µg/g dry weight and varied geographically, with the highest concentrations in the Northwest Territories followed by Nunavut and Yukon. Regression models at both spatial scales indicated diet (based on nitrogen stable isotope ratios) was the strongest explanatory variable of mercury concentrations in wolverine, with smaller though statistically significant contributions from landscape variables (soil organic carbon, percent cover of wet area, percent cover of perennial snow-ice) and distance to the Arctic Ocean coast. The carbon and nitrogen stable isotope ratios of wolverine muscle suggested greater mercury bioaccumulation could be associated with feeding on marine biota in coastal habitats. Landscape variables identified in the modelling may reflect habitat conditions which support enhanced methylmercury transfer to terrestrial biota. Spatially-explicit estimates of wet atmospheric deposition were positively correlated with wolverine mercury concentrations but this variable was not selected in the final regression models. These landscape patterns provide a basis for further research on underlying processes enhancing methylmercury uptake in high latitude terrestrial food webs.

Toxicological risk of mercury for fish and invertebrate prey in the Arctic.

We assessed the risks of mercury (Hg) to Arctic marine and freshwater fish by compiling published muscle Hg concentrations and information on tissue concentrations associated with adverse effects. The assessment included 333 groups of fish representing 35 genera and 14,002 individuals sampled from sites across the circumpolar Arctic. Mean or median Hg concentrations in fish muscle varied widely from 0.005 µg/g ww to a maximum of 2.2 µg/g ww. Results indicate that most (n = 139 of 333 or ~ 42%) Arctic fish are not at risk for Hg toxicity, based on the large number of fish mean or median muscle Hg concentrations below 0.1 µg/g ww. A smaller number of the identified groups (n = 76 of 333 or ~ 23%) of Arctic fish had mean or median Hg concentrations consistent with moderate (0.3-0.5 µg/g ww), high (0.5-2 µg/g ww), and severe risk (≥2 µg/g ww). Most of the fish with Hg concentrations in these risk categories were long-lived predators (e.g., non-anadromous Arctic char, northern pike, lake trout, Greenland halibut, Greenland shark). We also, for the first time, conducted a risk assessment of Arctic marine and freshwater invertebrates to evaluate the potential for Hg effects at lower trophic levels and to support risk assessment for Arctic fish. The vast majority (90%) of site-specific Hg or methylmercury (MeHg) concentrations in taxa of marine and freshwater invertebrates (n = 321) were < 0.5 µg/g dw, which is well below critical body residues of Hg in aquatic invertebrates associated with acute and sublethal effects determined in laboratory dosing studies. As the screening-level approach we carried out in the present study is not indicative of actual effects, more studies which directly evaluate the effects of Hg exposure in Arctic fish species are needed. The information here will be of use to Article 22 (Effectiveness Evaluation) of the Minamata Convention.

Wildfires trigger multi-decadal increases in sedimentation rate and metal loading to subarctic montane lakes.

We evaluated how two large wildfires affected the sedimentation rate and accumulation of lead (Pb), mercury (Hg), and cadmium (Cd) in sediment of four subarctic montane lakes in the Yukon, Canada. The wildfires occurred 60 and 20 years (1958, 1998) before sediment collection in 2018. Site-specific fire exposure was inferred from the charcoal accumulation histories in the lake sediments and the burned catchment area was determined from historical fire maps. The two major wildfires caused a two to five-fold increase in sedimentation rates and a two to eight-fold increase in sediment metal accumulation rates in Little Fox Lake. The mass accumulation rates of metals in Little Fox Lake sediment increased by a maximum of 2.7-4.7 mg Pb m-2 yr-1, 19-29 µg Hg m-2 yr-1 and 37-114 µg Cd m-2 yr-1 following wildfires. Modelling using elemental ratios of lithogenic sources suggested a large proportion of the Pb and Hg accumulating in post-fire sediment was from remobilized legacy anthropogenic pollution. In contrast, Cd fluxes were consistent with variation in catchment weathering. Impacts of wildfires were visible but more muted in the sediment of Little Braeburn Lake, whereas Fox Lake and Grayling Lake sediments showed little to no wildfire impact and served as a reference for external (long-range) metal deposition. Major changes to lake sediment geochemistry in Little Fox Lake were caused by the lack of vegetation and soil recovery in the catchment following the severe 1998 fire. Wildfire impacts were persistent in the lake more than 20 years after the last fire, with no sign of a return to pre-fire Pb, Hg, and Cd accumulation rates. This study shows that wildfires in northern montane catchments can significantly increase the rate of metal accumulation in affected lakes, thereby impeding recovery from reductions in anthropogenic air emissions of these metals.

Experimental investigation of short-term warming on arsenic flux from contaminated sediments of two well-oxygenated subarctic lakes.

Legacy arsenic (As) contamination from past mining operations remains an environmental concern in lakes of the Yellowknife area (Northwest Territories, Canada) due to its post-depositional mobility in sediment and potential for continued remobilization to surface waters. Warmer temperatures associated with climate change in this subarctic region may impact As internal loading from lake sediments either by a direct effect on sediment porewater diffusion rate or indirect effects on microbial metabolism and sediment redox conditions. This study assessed the influence of warmer temperatures on As diffusion from contaminated sediment of two lakes with contrasting sediment characteristics using an experimental incubation approach. Sediments from Yellowknife Bay (on Great Slave Lake) contained predominately clay and silt with low organic matter (10%) and high As content (1675 µg/g) while sediments of Lower Martin Lake had high organic matter content (~70%) and approximately half the As (822 µg/g). Duplicate sediment batches from each lake were incubated in a temperature-controlled chamber, and overlying water was kept well-oxygenated while As flux from sediment was measured during four weekly temperature treatments (7°C to 21°C, at ~5°C intervals). During the experiment, As diffused from sediment to overlying water in all cores and temperature treatments, with As fluxes ranging from 48-956 µg/m2/day. Arsenic fluxes were greater from Yellowknife Bay sediments, which had higher solid-phase As concentrations, compared to those of Lower Martin Lake. Short-term warming did not stimulate As flux from duplicate cores of either sediment type, in contrast with reported temperature enhancement in other published studies. We conclude that warmer temperatures were insufficient to strongly enhance sediment As diffusion into overlying oxic waters. These observations are relevant for evaluating climate-warming effects on sediment As mobility in subarctic lakes with little or no thermal stratification and a well-oxygenated water column.

Special issue on the AMAP 2021 assessment of mercury in the Arctic.

This Editorial presents an overview of the Special Issue on advances in Arctic mercury (Hg) science synthesized from the 2021 assessment of the Arctic Monitoring and Assessment Programme (AMAP). Mercury continues to travel to Arctic environments and threaten wildlife and human health in this circumpolar region. Over the last decade, progress has been achieved in addressing policy-relevant uncertainties in environmental Hg contamination. This includes temporal trends of Hg, its transport to and within the Arctic, methylmercury cycling, climate change influences, biological effects of Hg on fish and wildlife, human exposure to Hg, and forecasting of Arctic responses to different future scenarios of anthropogenic Hg emissions. In addition, important contributions of Indigenous Peoples to Arctic research and monitoring of Hg are highlighted, including through projects of knowledge co-production. Finally, policy-relevant recommendations are summarized for future study of Arctic mercury. This series of scientific articles presents comprehensive information relevant to supporting effectiveness evaluation of the United Nations Minamata Convention on Mercury.

Isotopic evidence for bioaccumulation of aerosol lead in fish and wildlife of western Canada.

Lead (Pb) is a toxic element which is released as a result of anthropogenic activities, and Pb stable isotope ratios provide a means to distinguish sources and transport pathways in receiving environments. In this study, isotopes of bioaccumulated Pb (204Pb, 206Pb, 207Pb, 208Pb) were examined for diverse terrestrial and aquatic biota from three areas in western Canada: (a) otter, marten, gulls, terns, and wood frogs in the Alberta Oil Sands Region (AOSR), (b) fish, plankton, and gulls of Great Slave Lake (Yellowknife, Northwest Territories), and (c) wolverine from the Yukon. Aquatic and terrestrial biota from different habitats and a broad geographic area showed a remarkable similarity in their Pb isotope composition (grand mean ± 1 standard deviation: 206Pb/207Pb = 1.189 ± 0.007, 208Pb/207Pb = 2.435 ± 0.009, n = 116). Comparisons with Pb isotope ratios of local sources and environmental receptors showed that values in biota were most similar to those of atmospheric Pb, either measured in local aerosols influenced by industrial activities in the AOSR or in lichens (an aerosol proxy) near Yellowknife and in the Yukon. Biotic Pb isotope ratios were different from those of local geogenic Pb. Although the Pb isotope measurements could not unambiguously identify the specific anthropogenic sources of atmospheric Pb in biota, initial evidence points to the importance of fossil fuels currently used in transportation and power generation. Further research should characterize bioavailable chemical species of Pb in aerosols and important emission sources in western Canada.

Arctic methylmercury cycling.

Anthropogenic mercury (Hg) undergoes long-range transport to the Arctic where some of it is transformed into methylmercury (MeHg), potentially leading to high exposure in some Arctic inhabitants and wildlife. The environmental exposure of Hg is determined not just by the amount of Hg entering the Arctic, but also by biogeochemical and ecological processes occurring in the Arctic. These processes affect MeHg uptake in biota by regulating the bioavailability, methylation and demethylation, bioaccumulation and biomagnification of MeHg in Arctic ecosystems. Here, we present a new budget for pools and fluxes of MeHg in the Arctic and review the scientific advances made in the last decade on processes leading to environmental exposure to Hg. Methylation and demethylation are key processes controlling the pool of MeHg available for bioaccumulation. Methylation of Hg occurs in diverse Arctic environments including permafrost, sediments and the ocean water column, and is primarily a process carried out by microorganisms. While microorganisms carrying the hgcAB gene pair (responsible for Hg methylation) have been identified in Arctic soils and thawing permafrost, the formation pathway of MeHg in oxic marine waters remains less clear. Hotspots for methylation of Hg in terrestrial environments include thermokarst wetlands, ponds and lakes. The shallow sub-surface enrichment of MeHg in the Arctic Ocean, in comparison to other marine systems, is a possible explanation for high MeHg concentrations in some Arctic biota. Bioconcentration of aqueous MeHg in bacteria and algae is a critical step in the transfer of Hg to top predators, which may be dampened or enhanced by the presence of organic matter. Variable trophic position has an important influence on MeHg concentrations among populations of top predator species such as ringed seal and polar bears distributed across the circumpolar Arctic. These scientific advances highlight key processes that affect the fate of anthropogenic Hg deposited to Arctic environments.

Climate change and mercury in the Arctic: Abiotic interactions.

Dramatic environmental shifts are occuring throughout the Arctic from climate change, with consequences for the cycling of mercury (Hg). This review summarizes the latest science on how climate change is influencing Hg transport and biogeochemical cycling in Arctic terrestrial, freshwater and marine ecosystems. As environmental changes in the Arctic continue to accelerate, a clearer picture is emerging of the profound shifts in the climate and cryosphere, and their connections to Hg cycling. Modeling results suggest climate influences seasonal and interannual variability of atmospheric Hg deposition. The clearest evidence of current climate change effects is for Hg transport from terrestrial catchments, where widespread permafrost thaw, glacier melt and coastal erosion are increasing the export of Hg to downstream environments. Recent estimates suggest Arctic permafrost is a large global reservoir of Hg, which is vulnerable to degradation with climate warming, although the fate of permafrost soil Hg is unclear. The increasing development of thermokarst features, the formation and expansion of thaw lakes, and increased soil erosion in terrestrial landscapes are increasing river transport of particulate-bound Hg and altering conditions for aquatic Hg transformations. Greater organic matter transport may also be influencing the downstream transport and fate of Hg. More severe and frequent wildfires within the Arctic and across boreal regions may be contributing to the atmospheric pool of Hg. Climate change influences on Hg biogeochemical cycling remain poorly understood. Seasonal evasion and retention of inorganic Hg may be altered by reduced sea-ice cover and higher chloride content in snow. Experimental evidence indicates warmer temperatures enhance methylmercury production in ocean and lake sediments as well as in tundra soils. Improved geographic coverage of measurements and modeling approaches are needed to better evaluate net effects of climate change and long-term implications for Hg contamination in the Arctic.