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The presence of toxic methylmercury (MeHg) in Arctic freshwater ecosystems and foodwebs is a potential health concern for northern Indigenous people. Addressing this issue requires a better understanding of MeHg production, fate during transport, and uptake into foodwebs. We used methylation assays and spatiotemporal surveys of MeHg concentrations, during the ice-covered and open water seasons, across a hydrologic continuum (composed of thaw seeps, lake/ponds, and a wetland) to identify Hg methylation hotspots and seasonal differences in MeHg cycling unique to Arctic ecosystems. Ponds and saturated wetland soils support methylation hotspots during the open water season, but subsequent export of MeHg to downstream ecosystems is limited by particle settling, binding of MeHg on soil organic matter, and/or demethylation in drier wetland soils. During the ice-covered season, MeHg concentrations in lake waters were approximately ten-fold greater than in summer; however, zooplankton MeHg concentrations were paradoxically five times lower at this time. Despite limited evidence of snow-phase methylation, the snowpack is an important MeHg reservoir. Changes in ice-cover duration will alter MeHg production and bioaccumulation in lakes, while increased thaw and surface water flow will likely result in higher methylation rates at the aquatic-terrestrial interface and more efficient downstream transport of MeHg.

Gaseous elemental mercury (Hg0) concentrations in the atmosphere have been increasing due to anthropogenic activities since the onset of colonial mining in the 17th century. However, accurate measu...

Mercury (Hg) is a global pollutant emitted to the atmosphere from anthropogenic sources, which have varied over time in response to increased industrialization and pollution control measures. Tree rings have shown promise for reconstructing past atmospheric Hg(0) concentrations to expand on the temporally and spatially limited data provided by the instrumental record, producing high-resolution data with absolutely dated chronologies. Here, we present a ∼400 year reconstruction of atmospheric Hg(0) based on white spruce (Picea glauca) tree rings from a pristine coastal area in Northwestern Canada (Mackenzie Delta, Northwest Territories). The tree-ring record shows that Hg concentrations did not begin to increase significantly above baseline until ∼1875, coinciding with increased industrialization in Europe and North America. Hg concentrations reached a maximum in the 1970s and subsequently declined until the end of the 20th century, which is consistent with the trends in modeled global tropospheric Hg(0) concentrations based on the latest Hg-emission inventories. However, unlike many other locations in the northern hemisphere, the Mackenzie Delta tree-ring record exhibits a rebound in Hg(0) concentrations since the turn of the century, likely reflecting the increase in upwind Asian industrial emissions. The relative enrichment in inferred modern atmospheric Hg(0) relative to preindustrial concentrations [enrichment factors (EF) = 1.54] is similar to other EF values obtained from tree rings, but lower than those based on models and sedimentary archives. Tree-ring Hg concentrations in the Mackenzie Delta were higher than at a continental site also located in northwestern Canada, suggesting that ocean Hg(0) evasion and permafrost slumping contribute to higher local atmospheric concentrations.

Mercury (Hg) is a global pollutant released from both natural and human sources. Here we compare long-term records of wet deposition loadings of total Hg (THg) in the open to dry deposition loadings of THg in throughfall and litterfall under four boreal mixedwood canopy types at the remote Experimental Lakes Area (ELA) in Northwestern Ontario, Canada. We also present long-term records of atmospheric concentrations of gaseous elemental (GEM), gaseous oxidized (GOM), and particle bound (PBM) Hg measured at the ELA. We show that dry THg loadings in throughfall and litterfall are 2.7 to 6.1 times greater than wet THg loadings in the open. GEM concentrations showed distinct monthly and daily patterns, correlating positively in spring and summer with rates of gross ecosystem productivity and respiration. GOM and PBM concentrations were less variable throughout the year but were highest in the winter, when concentrations of anthropogenically sourced particles and gases were also high. Forest fires, Arctic air masses, and road salt also impacted GEM, GOM, and PBM concentrations at the ELA. A nested GEOS-Chem simulation for the ELA region produced a dry/wet deposition ratio of >5, suggesting that the importance of dry deposition in forested regions can be reasonably modeled by existing schemes for trace gases.

Use of elemental mercury (Hg0) to enhance placer gold recovery is an effective method dating back centuries, but is associated with significant atmospheric Hg0 losses. This method was widely used in the Canadian Klondike region during most of the 20th century when the mining industry experienced rapid growth. While the health risks associated with Hg0 pollution are now well understood, few studies have assessed the environmental legacy of Hg0 use in the Klondike. We used an annually resolved Picea glauca tree-ring Hg record (1864–2015) to reconstruct and evaluate changes in local atmospheric Hg0 concentrations associated with gold production at the Bear Creek mining camp. Major temporal trends in the record are consistent with the scale of Bear Creek operations and are distinct from background trends at an unimpacted control site. Tree-ring Hg concentration increased most rapidly from 1923 to 1930, a period when several major mining operations were consolidated at Bear Creek. The highest Hg concentrations, ∼2.5× greater than pre-mining era, occurred in the 1930s, coinciding with maximum gold production at this site. Post-World War II economic factors adversely affected the industry, causing declining tree-ring Hg concentrations from 1939 to 1966. Closure of the Bear Creek camp in 1966 coincided with the strongest tree-ring Hg decline, although a return to background levels did not occur until the 1990s, likely due to re-emission of legacy Hg0 from contaminated soils. Finally, a robust increase was observed over the last decade, similar to other tree-ring Hg records in N.W. Canada, which is linked to rising Hg0 emissions in Asia. The Bear Creek tree-ring Hg record provides a unique opportunity to study the impact of Klondike gold mining on the local environment at annual resolution and demonstrates great potential to use Picea tree rings to study past changes in atmospheric Hg0 from local and global emissions. Main findings A 151-year long, annually resolved tree-ring Hg record was developed at a historic Klondike gold-mining site to investigate the influence of mining-related Hg0 emissions on the local atmosphere and environment. Compared to a control site, the tree-ring Hg record documents highly elevated atmospheric Hg0 concentrations during the period mining activities were ongoing at this site.

Across the Arctic, glaciers are melting and permafrost is thawing at unprecedented rates, releasing not only water to downstream aquatic systems, but also contaminants like mercury, archived in ice over centuries. Using concentrations from samples collected over 4 years and calibrated modeled hydrology, we calculated methylmercury (MeHg) and total mercury (THg) mass balances for Lake Hazen, the world's largest High Arctic lake by volume, for 2015 and 2016. Glacial rivers were the most important source of MeHg and THg to Lake Hazen, accounting for up to 53% and 94% of the inputs, respectively. However, due to the MeHg and THg being primarily particle-bound, Lake Hazen was an annual MeHg and THg sink. Exports of MeHg and THg out the Ruggles River outflow were consequently very low, but erosion and permafrost slumping downstream of the lake increased river MeHg and THg concentrations significantly before entering coastal waters in Chandler Fjord. Since 2001, glacial MeHg and THg inputs to Lake Hazen have increased by 0.01 and 0.400 kg yr

Snowpacks in the Alberta Oil Sands Region (AOSR) of Canada contain elevated loadings of methylmercury (MeHg; a neurotoxin that biomagnifies through foodwebs) due to oil sands related activities. At sites ranging from 0 to 134 km from the major AOSR upgrading facilities, we examined sources of MeHg by quantifying potential rates of MeHg production in snowpacks and melted snow using mercury stable isotope tracer experiments, as well as quantifying concentrations of MeHg on particles in snowpacks (pMeHg). At four sites, methylation rate constants were low in snowpacks (km = 0.001–0.004 d–1) and nondetectable in melted snow, except at one site (km = 0.0007 d–1). The ratio of methylation to demethylation varied between 0.3 and 1.5, suggesting that the two processes are in balance and that in situ production is unlikely an important net source of MeHg to AOSR snowpacks. pMeHg concentrations increased linearly with distance from the upgraders (R2 = 0.71, p < 0.0001); however, snowpack total particle and pMeHg lo...

Elevated biological concentrations of methylmercury (MeHg), a bioaccumulative neurotoxin, are observed throughout the Arctic Ocean, but major sources and degradation pathways in seawater are not well understood. We develop a mass budget for mercury species in the Arctic Ocean based on available data since 2004 and discuss implications and uncertainties. Our calculations show that high total mercury (Hg) in Arctic seawater relative to other basins reflect large freshwater inputs and sea ice cover that inhibits losses through evasion. We find that most net MeHg production (20 Mg a−1) occurs in the subsurface ocean (20–200 m). There it is converted to dimethylmercury (Me2Hg: 17 Mg a−1), which diffuses to the polar mixed layer and evades to the atmosphere (14 Mg a−1). Me2Hg has a short atmospheric lifetime and rapidly degrades back to MeHg. We postulate that most evaded Me2Hg is redeposited as MeHg and that atmospheric deposition is the largest net MeHg source (8 Mg a−1) to the biologically productive surface ocean. MeHg concentrations in Arctic Ocean seawater are elevated compared to lower latitudes. Riverine MeHg inputs account for approximately 15% of inputs to the surface ocean (2.5 Mg a−1) but greater importance in the future is likely given increasing freshwater discharges and permafrost melt. This may offset potential declines driven by increasing evasion from ice-free surface waters. Geochemical model simulations illustrate that for the most biologically relevant regions of the ocean, regulatory actions that decrease Hg inputs have the capacity to rapidly affect aquatic Hg concentrations.

Perfluoroalkyl substances (PFASs) are synthetic environmentally-persistent pollutants that are amenable to long-range transport and accumulation in remote Arctic ecosystems. In this study, historical inventories of twenty-three PFASs (i.e. C4-C14, C16 perfluoroalkane carboxylic acids (PFCAs); C4, C6-C8, C10 perfluoroalkane sulfonic acids (PFSAs); perfluoro-4-ethyl-cyclohexane sulfonic acid (PFECHS); dodecafluoro-3H-4,8-dioxanonanoic acid (ADONA); 8-chloro-perfluoro-1-octane sulfonic acid (8-Cl-PFOS); chlorinated polyfluorinated ether sulfonic acids (Cl-PFESAs) including 9-chlorohexadecafluoro-3-oxanonane-1-sulfonic acid (6:2 Cl-PFESA) and 11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid (8:2 Cl-PFESA); as well as perfluorooctane sulfonamide (FOSA)) are determined in two intact sediment cores collected from Lake Hazen, located in northern Ellesmere Island at 82° N in 2012 and Lake B35, located in central Nunavut at 64° N in 2009. In Lake Hazen, fluxes of perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), perfluorobutane sulfonic acid (PFBS), and perfluorooctane sulfonic acid (PFOS) increased during 1963-2011. In Lake B35, fluxes of perfluoroheptanoic acid (PFHpA), PFOA, perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUnDA) increased during 1952-2009. The temporal trends for PFASs in Lake Hazen and Lake B35 sediments are consistent with the continuous annual delivery of PFASs to the Arctic of Canada. Temporal trends in sediment cores appear to follow historical market changes in PFAS manufacturing inventory. The doubling time of PFAS fluxes are faster in Lake Hazen sediments than Lake B35 sediments. In Lake Hazen, this may be attributed to the enhanced delivery of sediment and historically-archived PFASs promoted by climate-induced glacier melting in the Lake Hazen watershed post-2005. Exponentially increasing PFAS temporal trends in High and Low Arctic lakes in Canada stress the importance of developing effective global regulatory policies for PFAS manufacturing and highlights the potential for climate change-induced contaminant release from melting glaciers in the Arctic.

A warming climate is rapidly changing the distribution and exchanges of carbon within high Arctic ecosystems. Few data exist, however, which quantify exchange of both carbon dioxide (CO2) and methane (CH4) between the atmosphere and freshwater systems, or estimate freshwater contributions to total catchment exchange of these gases, in the high Arctic. During the summers of 2005 and 2007–2012, we quantified CO2 and CH4 concentrations in, and atmospheric exchange with, common freshwater systems in the high Arctic watershed of Lake Hazen, Nunavut, Canada. We identified four types of biogeochemically distinct freshwater systems in the watershed; however mean CO2 concentrations (21–28 µmol L−1) and atmospheric exchange (−0.013 to +0.046 g C–CO2 m−2 day−1) were similar between these systems. Seasonal flooding of ponds bordering Lake Hazen generated considerable CH4 emissions to the atmosphere (+0.008 g C–CH4 m−2 day−1), while all other freshwater systems were minimal emitters of this gas (4 m−2 day−1). When using ecosystem-cover classification mapping and data from previous studies, we found that freshwaters were unimportant contributors to total watershed carbon exchange, in part because they covered less than 10 % of total area in the watershed. High Arctic watersheds are experiencing warmer and wetter climates than in the past, which may have implications for moisture availability, landscape cover, and the exchange of CO2 and CH4 of underproductive but expansive polar semidesert ecosystems.

Tree-rings are a promising high-resolution archive for gaseous atmospheric mercury (composed primarily of Hg0) reconstruction, but the influence of cambial age (ring number from pith) and tree-specific differences are uncertainties with potential implications for interpreting tree-ring Hg signals. We address these uncertainties and reconstruct the last 400 years of Hg0 change using a tree-ring Hg data set from 20 white spruce ( Picea glauca) trees from a pristine site in central Yukon. Cambial age has no significant influence on tree-ring Hg concentration, but tree-specific differences in mean concentration are prevalent and must be normalized to a common mean to accurately constrain long-term trends in the mean tree-ring Hg record. Our record shows stable, low Hg0 concentrations prior to ∼1750 CE, a persistent rise from ∼1750-1950 (increasing more rapidly post-1850), a pause from ∼1951-1975, and then a resumed increase to record-high levels at present. This general pattern is reflected in other proxy-based Hg reconstructions worldwide. This study provides a novel long-term Hg0 reconstruction in the Western subarctic from one of the most widely distributed boreal tree species in North America and, therefore this proxy may also hold potential for investigating broader spatial patterns in Hg0 cycling across the subarctic and northern boreal forest.

Long-range atmospheric transport and deposition are important sources of mercury (Hg) to Arctic aquatic and terrestrial ecosystems. We review here recent progress made in the study of the transport, transformation, deposition and reemission of atmospheric Hg in the Canadian Arctic, focusing on field measurements (see Dastoor et al., this issue for a review of modeling studies on the same topics). Redox processes control the speciation of atmospheric Hg, and thus impart an important influence on Hg deposition, particularly during atmospheric mercury depletion events (AMDEs). Bromine radicals were identified as the primary oxidant of atmospheric Hg during AMDEs. Since the start of monitoring at Alert (NU) in 1995, the timing of peak AMDE occurrence has shifted to earlier times in the spring (from May to April) in recent years, and while AMDE frequency and GEM concentrations are correlated with local meteorological conditions, the reasons for this timing-shift are not understood. Mercury is subject to various post-depositional processes in snowpacks and a large portion of deposited oxidized Hg can be reemitted following photoreduction; how much Hg is deposited and reemitted depends on geographical location, meteorological, vegetative and sea-ice conditions, as well as snow chemistry. Halide anions in the snow can stabilize Hg, therefore it is expected that a smaller fraction of deposited Hg will be reemitted from coastal snowpacks. Atmospheric gaseous Hg concentrations have decreased in some parts of the Arctic (e.g., Alert) from 2000 to 2009 but at a rate that was less than that at lower latitudes. Despite numerous recent advances, a number of knowledge gaps remain, including uncertainties in the identification of oxidized Hg species in the air (and how this relates to dry vs. wet deposition), physical–chemical processes in air, snow and water—especially over sea ice—and the relationship between these processes and climate change.

Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is incomplete because atmospheric sources and sinks of MMHg are still unclear. We sampled air in the Canadian Arctic marine boundary layer to quantify, for the first time, atmospheric concentrations of methylated Hg species (both MMHg and dimethylmercury (DMHg)), and, estimate the importance of atmospheric deposition as a source of MMHg to Arctic land- and sea-scapes. Overall atmospheric MMHg and DMHg concentrations (mean ± SD) were 2.9 ± 3.6 and 3.8 ± 3.1 (n = 37) pg m(-3), respectively. Concentrations of methylated Hg species in the marine boundary layer varied significantly among our sites, with a predominance of MMHg over Hudson Bay (HB), and DMHg over Canadian Arctic Archipelago (CAA) waters. We concluded that DMHg is of marine origin and that primary production rate and sea-ice cover are major drivers of its concentration in the Canadian Arctic marine boundary layer. Summer wet deposition rates of atmospheric MMHg, likely to be the product of DMHg degradation in the atmosphere, were estimated at 188 ± 117.5 ng m(-2) and 37 ± 21.7 ng m(-2) for HB and CAA, respectively, sustaining MMHg concentrations available for biomagnification in the pelagic food web.

There has been increasing concern about mercury (Hg) levels in marine and freshwater organisms in the Arctic, due to the importance of traditional country foods such as fish and marine mammals to the diet of Northern Peoples. Due to its toxicity and ability to bioaccumulate and biomagnify in food webs, methylmercury (MeHg) is the form of Hg that is of greatest concern. The main sources of MeHg to Arctic aquatic ecosystems, the processes responsible for MeHg formation and degradation in the environment, MeHg bioaccumulation in Arctic biota and the human health implications for Northern Peoples are reviewed here. In Arctic marine ecosystems, Hg(II) methylation in the water column, rather than bottom sediments, is the primary source of MeHg, although a more quantitative understanding of the role of dimethylmercury (DMHg) as a MeHg source is needed. Because MeHg production in marine waters is limited by the availability of Hg(II), predicted increases in Hg(II) concentrations in oceans are likely to result in higher MeHg concentrations and increased exposure to Hg in humans and wildlife. In Arctic freshwaters, MeHg concentrations are a function of two antagonistic processes, net Hg(II) methylation in bottom sediments of ponds and lakes and MeHg photodemethylation in the water column. Hg(II) methylation is controlled by microbial activity and Hg(II) bioavailability, which in turn depend on interacting environmental factors (temperature, redox conditions, organic carbon, and sulfate) that induce nonlinear responses in MeHg production. Methylmercury bioaccumulation–biomagnification in Arctic aquatic food webs is a function of the MeHg reservoir in abiotic compartments, as well as ecological considerations such as food-chain length, growth rates, life-history characteristics, feeding behavior, and trophic interactions. Methylmercury concentrations in Arctic biota have increased significantly since the onset of the industrial age, and in some populations of fish, seabirds, and marine mammals toxicological thresholds are being exceeded. Due to the complex connection between Hg exposure and human health in Northern Peoples—arising from the dual role of country foods as both a potential Hg source and a nutritious, affordable food source with many physical and social health benefits—-reductions in anthropogenic Hg emissions are seen as the only viable long-term solution.

High Arctic landscapes are essentially vast cold deserts interspersed with streams, ponds and wetlands. These landscapes may be important consumers and sources of the greenhouse gas methane (CH4), though few measurements exist from this region. To quantify the flux of CH4 (FCH4) between the atmosphere and high Arctic landscapes on northern Ellesmere Island, Canada, we made static chamber measurements over five and three growing seasons at a desert and wetland, respectively, and eddy covariance (EC) measurements at a wetland in 2012. Chamber measurements revealed that, during the growing season, desert soils consumed CH4 (−1.37 &pm; 0.06 mg-CH4 m−2 d−1), whereas the wetland margin emitted CH4 (+0.22 ± 0.14 mg-CH4 m−2 d−1). Desert CH4 consumption rates were positively associated with soil temperature among years, and were similar to temperate locations, likely because of suitable landscape conditions for soil gas diffusion. Wetland FCH4 varied closely with stream discharge entering the wetland and hence extent of soil saturation. Landscape-scale FCH4 measured by EC was +1.27 ± 0.18 mg-CH4 m−2 d−1 and varied with soil temperature and carbon dioxide flux. FCH4 measured using EC was higher than using chambers because EC measurements incorporated a larger, more saturated footprint of the wetland. Using EC FCH4 and quantifying the mass of CH4 entering and exiting the wetland in stream water, we determined that methanogenesis within wetland soils was the dominant source of FCH4. Low FCH4 at the wetland was likely due to a shallow organic soil layer, and thus limited carbon resources for methanogens. Considering the prevalence of dry soils in the high Arctic, our results suggest that these landscapes cannot be overlooked as important consumers of atmospheric CH4.

A warming climate is rapidly changing the distribution and exchanges of carbon within high Arctic ecosystems. Few data exist, however, which quantify exchange of both carbon dioxide (CO2) and methane (CH4) between the atmosphere and freshwater systems, or estimate freshwater contributions to total catchment exchange of these gases, in the high Arctic. During the summers of 2005 and 2007–2012, we quantified CO2 and CH4 concentrations in, and atmospheric exchange with, common freshwater systems in the high Arctic watershed of Lake Hazen, Nunavut, Canada. We identified four types of biogeochemically-distinct freshwater systems in the watershed, however mean CO2 concentrations (21–28 μmol L−1) and atmospheric exchange (−0.013–0.046 g C-CO2 m−2 d−1) were similar between these systems. Seasonal flooding of ponds bordering Lake Hazen generated considerable CH4 emissions to the atmosphere (0.008 g C-CH4 m−2 d−1), while all other freshwater systems were minimal emitters of this gas (< 0.001 g C-CH4 m−2 d−1). Measurements made on terrestrial landscapes in the same watershed between 2008–2012 determined that the near-barren polar semidesert was a very weak consumer of atmospheric CO2 (−0.004 g C-CO2 m−2 d−1), but an important consumer of atmospheric CH4 (−0.001 g C-CH4 m−2 d−1). Alternatively, meadow wetlands were very productive consumers of atmospheric CO2 (−0.96 g C-CO2 m−2 d−1) but relatively weak emitters of CH4 to the atmosphere (0.001 g C-CH4m−2 d−1). When using ecosystem-cover classification mapping, we found that freshwaters were unimportant contributors to total watershed carbon exchange, in part because they covered less than 10 % of total cover in the watershed. High Arctic watersheds are experiencing warmer and wetter climates than in the past, which may have implications for the net uptake of carbon greenhouse gases by currently underproductive polar semidesert and freshwater systems.

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

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8-40 ng MeHg m(-2) d(-1)) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029-0.051 ng MeHg m(-2) d(-1)), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0-33 ng MeHg m(-2) d(-1)), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

Although it has been previously shown that forest canopies significantly increase the total deposition of Hg to watersheds, sources and fates of atmospherically deposited MeHg in particular remain poorly understood. In this study, net loadings of MeHg to a watershed were quantified, and the retention and (photo)reduction of MeHg on foliage were measured using unique stable Hg isotope experiments. Annual loadings of MeHg in throughfall (0.34 ± 0.01 to 0.60 ± 0.16 mg ha⁻¹ yr⁻¹) and litterfall (0.77 ± 0.07 to 0.97 ± 0.34 mg ha⁻¹ yr⁻¹) were collectively 3-4 times higher under different forest canopies than loadings of MeHg in the open (0.41 mg ha⁻¹ yr⁻¹), suggesting dry deposition of MeHg to forest canopies. Using Me¹⁹⁹Hg, we found that a portion of MeHg wet deposited to forest canopies is retained on foliage over time, eventually contributing to MeHg in litterfall. Average half-lives (t½) of Me¹⁹⁹Hg on spruce, jack pine, and birch foliage were 204 ± 66, 187 ± 101, and 8 ± 3 days, respectively. We also found using Me¹⁹⁹Hg that following wet deposition, MeHg is rapidly (photo)reduced to ¹⁹⁹Hg(0) on canopy foliage, which then evades to the atmosphere. We were unable to quantify concentrations of particulate-bound MeHg (p-MeHg) in the air using vacuum pumps and quartz microfiber air sampling filters, despite the possibility that p-MeHg does exist in small quantities. As a result, the source of dry deposited MeHg remains partially elusive.

Monomethylmercury is a neurotoxin that accumulates in marine organisms. Incubation experiments suggest that methylation of inorganic mercury accounts for around half of the monomethylmercury present in polar marine waters.

Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury (MeHg) in freshwater lakes. However, we possess little mechanistic knowledge of this important biogeochemical process with regard to, for instance, the role of ultraviolet (UV) radiation versus visible light in mediating MeHg PD. This information is critical to correctly model MeHg PD at the whole-lake level, since wavelengths in the UV and visible regions of the solar spectrum are attenuated at very different rates in the water column of lakes. Furthermore, the established methodology for quantifying MeHg PD requires the addition of a MeHg spike, which often increases the concentration of ambient MeHg by 1 to 2 orders of magnitude; however, the assumption that the MeHg spike behaves like ambient MeHg has never been verified. We quantified MeHg PD rates using an isotopically enriched Me199Hg tracer added to lake waters already containing high concentrations of ambient MeHg, allowing us to simultaneously monitor the decomposition rate of the spike and ambient MeHg. Experiments were conducted at the Experimental Lakes Area to quantify the first-order rate constant (k(pd)) of MeHg PD in samples exposed to (1) full solar radiation, (2) UV-A and visible light (i.e., with UV-B blocked), or (3) visible light only. We demonstrate for the first time that the use of a MeHg spike to quantify PD rates is appropriate since spike and ambient MeHg-both in samples with and without a spike of Me199Hg--are photodemethylated at the same rate. We also show that rates of MeHg PD are reduced by an order of magnitude in the absence of UV radiation and that to correctly model MeHg PD at the whole-lake scale, both UV and visible light mediated MeHg PD rates must be independently calculated using the light-specific rate constants (k(pd-UWB), k(pd.UVA), k(pd-VIS)). By examining modeled a real MeHg PD fluxes, we observed that UV radiation accounts for 58% and 79% of MeHg PD activity in a clear and colored lake, respectively. Finally, we demonstrate that correcting k(pd-overall) for the attenuation of solar radiation by Teflon bottles, which are normally used for MeHg PD experiments, increases the measured value of 3.69 x 10(-3) m2 E(-1) to 4.41 x 10(-3) m2 E(-1).

Although there is now a general consensus among mercury (Hg) biogeochemists that increased atmospheric inputs of inorganic Hg(II) to lakes and watersheds can result in increased methylmercury (MeHg) concentrations in fish, researchers still lack kinetic data describing the movement of Hg from the atmosphere, through watershed and lake ecosystems, and into fish. The use of isotopically enriched Hg species in environmental studies now allows experimentally applied new Hg to be distinguished from ambient Hg naturally present in the system. Four different enriched stable Hg(II) isotope "spikes" were applied sequentially over four years to the ground vegetation of a microcatchment at the Experimental Lakes Area (ELA) in the remote boreal forest of Canada to examine retention of Hg(II) following deposition. Areal masses of the spikes and ambient THg (all forms of Hg in a sample) were monitored for eight years, and the pattern of spike retention was used to estimate retention of newly deposited ambient Hg within the ground vegetation pool. Fifty to eighty percent of applied spike Hg was initially retained by ground vegetation. The areal mass of spike Hg declined exponentially over time and was best described by a first-order process with constants(k) ranging between 9.7 x 10(-40 day(-1) and 11.6 x 10(-4) day(-1). Average halflife (t1/2) of spike Hg within the ground vegetation pool (+/-S.D.) was 704 +/- 52 days. This retention of new atmospheric Hg(II) by vegetation delays movement of new Hg(II) into soil, runoff, and finally into adjacent lakes. Ground-applied Hg(II) spikes were not detected in tree foliage and litterfall, indicating that stomatal and/or root uptake of previously deposited Hg (i.e., "recycled" from ground vegetation or soil Hg pools) were likely not large sources of foliar Hg under these experimental conditions.

Caribou, which rely on lichens as forage, are a dietary source of monomethylmercury (MMHg) to many of Canada's Arctic Aboriginal people. However, little is understood about the sources of MMHg to lichens in the High Arctic. We quantified MMHg, total mercury (THg) and other chemical parameters (e.g., marine and crustal elements, δ(13)C, δ(15)N, organic carbon, calcium carbonate) in lichen and soil samples collected along transects extending from the coast on Bathurst and Devon islands, Nunavut, to determine factors driving lichen MMHg and THg concentrations in the High Arctic. Lichen MMHg and THg concentrations ranged from 1.41 to 17.1 ng g(-1) and from 36.0 to 361 ng g(-1), respectively. Both were highly enriched over concentrations in underlying soils, indicating a predominately atmospheric source of Hg in lichens. However, MMHg and THg enrichment at coastal sites on Bathurst Island was far greater than on Devon Island. We suggest that this variability can be explained by the proximity of the Bathurst Island transect to several polynyas, which promote enhanced Hg deposition to adjacent landscapes through various biogeochemical processes. This study is the first to clearly show a strong marine influence on MMHg inputs to coastal terrestrial food webs with implications for MMHg accumulation in caribou and the health of the people who depend on them as part of a traditional diet.

A review of mercury in the Canadian Arctic with a focus on field measurements is presented in part I (see Steffen et al., this issue). Here we provide insights into the dynamics of mercury in the Canadian Arctic from new and published mercury modeling studies using Environment Canada's mercury model. The model simulations presented in this study use global anthropogenic emissions of mercury for the period 1995–2005. The most recent modeling estimate of the net gain of mercury from the atmosphere to the Arctic Ocean is 75 Mg year− 1 and the net gain to the terrestrial ecosystems north of 66.5° is 42 Mg year− 1. Model based annual export of riverine mercury from North American, Russian and all Arctic watersheds to the Arctic Ocean are in the range of 2.8–5.6, 12.7–25.4 and 15.5–31.0 Mg year− 1, respectively. Analysis of long-range transport events of Hg at Alert and Little Fox Lake monitoring sites indicates that Asia contributes the most ambient Hg to the Canadian Arctic followed by contributions from North America, Russia, and Europe. The largest anthropogenic Hg deposition to the Canadian Arctic is from East Asia followed by Europe (and Russia), North America, and South Asia. An examination of temporal trends of Hg using the model suggests that changes in meteorology and changes in anthropogenic emissions equally contribute to the decrease in surface air elemental mercury concentrations in the Canadian Arctic with an overall decline of ~ 12% from 1990 to 2005. A slow increase in net deposition of Hg is found in the Canadian Arctic in response to changes in meteorology. Changes in snowpack and sea-ice characteristics and increase in precipitation in the Arctic related with climate change are found to be primary causes for the meteorology-related changes in air concentrations and deposition of Hg in the region. The model estimates that under the emissions reduction scenario of worldwide implementation of the best emission control technologies by 2020, mercury deposition could potentially be reduced by 18–20% in the Canadian Arctic.

Atmospheric deposition of metals originating from a variety of sources, including bitumen upgrading facilities and blowing dusts from landscape disturbances, is of concern in the Athabasca oil sands region of northern Alberta, Canada. Mercury (Hg) is of particular interest as methylmercury (MeHg), a neurotoxin which bioaccumulates through foodwebs, can reach levels in fish and wildlife that may pose health risks to human consumers. We used spring-time sampling of the accumulated snowpack at sites located varying distances from the major developments to estimate winter 2012 Hg loadings to a ∼20 000 km(2) area of the Athabasca oil sands region. Total Hg (THg; all forms of Hg in a sample) loads were predominantly particulate-bound (79 ± 12%) and increased with proximity to major developments, reaching up to 1000 ng m(-2). MeHg loads increased in a similar fashion, reaching up to 19 ng m(-2) and suggesting that oil sands developments are a direct source of MeHg to local landscapes and water bodies. Deposition maps, created by interpolation of measured Hg loads using geostatistical software, demonstrated that deposition resembled a bullseye pattern on the landscape, with areas of maximum THg and MeHg loadings located primarily between the Muskeg and Steepbank rivers. Snowpack concentrations of THg and MeHg were significantly correlated (r = 0.45-0.88, p0.01) with numerous parameters, including total suspended solids (TSS), metals known to be emitted in high quantities from the upgraders (vanadium, nickel, and zinc), and crustal elements (aluminum, iron, and lanthanum), which were also elevated in this region. Our results suggest that at snowmelt, a complex mixture of chemicals enters aquatic ecosystems that could impact biological communities of the oil sands region.

The Canadian Arctic has vast freshwater resources, and fish are important in the diet of many Northerners. Mercury is a contaminant of concern because of its potential toxicity and elevated bioaccumulation in some fish populations. Over the last decade, significant advances have been made in characterizing the cycling and fate of mercury in these freshwater environments. Large amounts of new data on concentrations, speciation and fluxes of Hg are provided and summarized for water and sediment, which were virtually absent for the Canadian Arctic a decade ago. The biogeochemical processes that control the speciation of mercury remain poorly resolved, including the sites and controls of methylmercury production. Food web studies have examined the roles of Hg uptake, trophic transfer, and diet for Hg bioaccumulation in fish, and, in particular, advances have been made in identifying determinants of mercury levels in lake-dwelling and sea-run forms of Arctic char. In a comparison of common freshwater fish species that were sampled across the Canadian Arctic between 2002 and 2009, no geographic patterns or regional hotspots were evident. Over the last two to four decades, Hg concentrations have increased in some monitored populations of fish in the Mackenzie River Basin while other populations from the Yukon and Nunavut showed no change or a slight decline. The different Hg trends indicate that the drivers of temporal change may be regional or habitat-specific. The Canadian Arctic is undergoing profound environmental change, and preliminary evidence suggests that it may be impacting the cycling and bioaccumulation of mercury. Further research is needed to investigate climate change impacts on the Hg cycle as well as biogeochemical controls of methylmercury production and the processes leading to increasing Hg levels in some fish populations in the Canadian Arctic.

Methylmercury (MeHg) is a potent neurotoxin that has been demonstrated to biomagnify in Arctic freshwater foodwebs to levels that may be of concern to Inuit peoples subsisting on freshwater fish, for example. The key process initiating the bioaccumulation and biomagnification of MeHg in foodwebs is the methylation of inorganic Hg(II) to form MeHg, and ultimately how much MeHg enters foodwebs is controlled by the production and availability of MeHg in a particular water body. We used isotopically enriched Hg stable isotope tracers in sediment core incubations to measure potential rates of Hg(II) methylation and investigate the controls on MeHg production in High Arctic wetland ponds in the Lake Hazen region of northern Ellesmere Island (Nunavut, Canada). We show here that MeHg concentrations in sediments are primarily controlled by the sediment methylation potential and the quantity of Hg(II) available for methylation, but not by sediment demethylation potential. Furthermore, MeHg concentrations in pond waters are controlled by MeHg production in sediments, overall anaerobic microbial activity, and photodemethylation in the water column.

Distribution of total mercury (THg), gaseous elemental Hg(0) (GEM), monomethyl Hg (MMHg), and dimethyl Hg (DMHg) was examined in marine waters of the Canadian Arctic Archipelago (CAA), Hudson Strait, and Hudson Bay. Concentrations of THg were low throughout the water column in all regions sampled (mean +/- standard deviation; 0.40 +/- 0.47 ng L(-1)). Concentrations of MMHg were also generally low atthe surface (23.8 +/- 9.9 pg L(-1)); however at mid- and bottom depths, MMHg was present at concentrations sufficient to initiate bioaccumulation of MMHg through Arctic marine foodwebs (maximum 178 pg L(-1); 70.3 +/- 37.3 pg L(-1)). In addition, at mid- and bottom depths, the % of THg that was MMHg was high (maximum 66%; 28 +/- 16%), suggesting that active methylation of inorganic Hg(II) occurs in deep Arctic marine waters. Interestingly, there was a constant, near 1:1, ratio between concentrations of MMHg and DMHg at all sites and depths, suggesting that methylated Hg species are in equilibrium with each other and/or are produced by similar processes throughout the water column. Our results also demonstrate that oceanographic processes, such as water regeneration and vertical mixing, affect Hg distribution in marine waters. Vertical mixing, for example, likely transported MMHg and DMHg upward from production zones at some sites, resulting in elevated concentrations of these species in surface waters (up to 68.0 pg L(-1)) where primary production and thus uptake of MMHg by biota is potentially highest. Finally, calculated instantaneous ocean-atmosphere fluxes of gaseous Hg species demonstrated that Arctic marine waters are a substantial source of DMHg and GEM to the atmosphere (27.3 +/- 47.8 and 130 +/- 138 ng m(-2) day(-1), respectively) during the ice-free season.

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L(-1)), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L(-1)), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 +/- 36 pg L(-1)), suggesting that open water regions such as polynyas and ice leads were a net source of approximately 130 +/- 30 ng Hg m(-2) day(-1) to the atmosphere. We also found 11.1 +/- 4.1 pg L(-1) of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then resultin MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Cl- concentrations in snowpacks and concentrations of THg. We hypothesize that as Cl- concentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cl- and deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha(-1) and 0.03 mg MMHg ha(-1)) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha(-1)). Therefore, most Arctic snowpacks contribute