Winter Dust Storms Impact the Physical and Biogeochemical Functioning of a Large High Arctic Lake.

We found that a winter of abnormally low snowfall and numerous dust storms from eolian processes acting on exposed landscapes (including a major 4-day dust storm while onsite in May 2014) caused a cascade of impacts on the physical, chemical, and ecological functioning of the largest lake by volume in the High Arctic (Lake Hazen; Nunavut, Canada). MODIS imagery revealed that dust deposited in snowpacks on the lake's ice acted as light-absorbing impurities (LAIs), reducing surface reflectance and increasing surface temperatures relative to normal snowpack years, causing early snowmelt and drainage of meltwaters into the lake. LAIs remaining on the ice surface melted into the ice, causing premature candling and one of the earliest ice-offs and longest ice-free seasons on record for Lake Hazen. Meltwater inputs from snowpacks resulted in dilution of dissolved, and increased concentration of particulate bound, chemical species in Lake Hazen's upper water column. Spring inputs of nutrients increased both heterotrophy and algal productivity under the surface ice following snowmelt, with a net consumption of dissolved oxygen. As climate change continues to alter High Arctic temperatures and precipitation patterns, we can expect further changes in dust storm frequency and severity with corresponding impacts for freshwater ecosystems.

Proglacial freshwaters are significant and previously unrecognized sinks of atmospheric CO2.

Carbon dioxide (CO2) emissions from freshwater ecosystems are almost universally predicted to increase with climate warming. Glacier-fed rivers and lakes, however, differ critically from those in nonglacierized catchments in that they receive little terrestrial input of organic matter for decomposition and CO2 production, and transport large quantities of easily mobilized comminuted sediments available for carbonate and silicate weathering reactions that can consume atmospheric CO2 We used a whole-watershed approach, integrating concepts from glaciology and limnology, to conclusively show that certain glacier-fed freshwater ecosystems are important and previously overlooked annual CO2 sinks due to the overwhelming influence of these weathering reactions. Using the glacierized Lake Hazen watershed (Nunavut, Canada, 82°N) as a model system, we found that weathering reactions in the glacial rivers actively consumed CO2 up to 42 km downstream of glaciers, and cumulatively transformed the High Arctic's most voluminous lake into an important CO2 sink. In conjunction with data collected at other proglacial freshwater sites in Greenland and the Canadian Rockies, we suggest that CO2 consumption in proglacial freshwaters due to glacial melt-enhanced weathering is likely a globally relevant phenomenon, with potentially important implications for regional annual carbon budgets in glacierized watersheds.

Methylmercury Transport and Fate Shows Strong Seasonal and Spatial Variability along a High Arctic Freshwater Hydrologic Continuum.

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.

Contrasting the ecological effects of decreasing ice cover versus accelerated glacial melt on the High Arctic's largest lake.

Lake Hazen, the High Arctic's largest lake, has received an approximately 10-fold increase in glacial meltwater since its catchment glaciers shifted from net mass gain to net mass loss in 2007 common era (CE), concurrent with recent warming. Increased glacial meltwater can alter the ecological functioning of recipient aquatic ecosystems via changes to nutrient budgets, turbidity and thermal regimes. Here, we examine a rare set of five high-resolution sediment cores collected in Lake Hazen between 1990 and 2017 CE to investigate the influence of increased glacial meltwater versus alterations to lake ice phenology on ecological change. Subfossil diatom assemblages in all cores show two major shifts over the past approximately 200 years including: (i) a proliferation of pioneering, benthic taxa at approximately 1900 CE from previously depauperate populations; and (ii) a rise in planktonic taxa beginning at approximately 1980 CE to present-day dominance. The topmost intervals from each sequentially collected core provide exact dates and demonstrate that diatom regime shifts occurred decades prior to accelerated glacial inputs. These data show that diatom assemblages in Lake Hazen are responding primarily to intrinsic lake factors linked to decreasing duration of lake ice and snow cover rather than to limnological impacts associated with increased glacial runoff.

Glacial Melt Inputs of Organophosphate Ester Flame Retardants to the Largest High Arctic Lake.

Organophosphate esters (OPEs) have been detected in the Arctic environment, but the influence of glacial melt on the environmental behavior of OPEs in recipient Arctic aquatic ecosystems is still unknown. In this study, water samples were collected from Lake Hazen (LH) and its tributaries to investigate the distribution of 14 OPEs in LH and to explore the input of OPEs from glacial rivers to LH and the output of OPEs from LH in 2015 and 2018. Σ14OPE concentrations in water of LH were lower than glacial rivers and its outflow, the Ruggles River. In 2015, a high melt year, we estimated that glacial rivers contributed 7.0 ± 3.2 kg OPEs to LH, compared to a 16.5 ± 0.3 kg OPEs output by the Ruggles River, suggesting that residence time and/or additional inputs via direct wet and dry deposition and permafrost melt likely result in OPE retention in the LH watershed. In 2018, a lower melt year, Σ14OPE concentrations in glacial rivers were much lower, indicating that the rate of glacier melt may govern, in part, the concentrations of OPEs in the tributaries of LH. This study highlights long-range transport of OPEs, their deposition in Arctic glaciers, landscapes, and lakes.

Fate and Transport of Perfluoroalkyl Substances from Snowpacks into a Lake in the High Arctic of Canada.

The delivery of perfluoroalkyl substances (PFAS) from snowpacks into Lake Hazen, located on Ellesmere Island (Nunavut, Canada, 82° N) indicates that annual atmospheric deposition is a major source of PFAS that undergo complex cycling in the High Arctic. Perfluoroalkyl carboxylic acids (PFCA) in snowpacks display odd-even concentration ratios characteristic of long-range atmospheric transport and oxidation of volatile precursors. Major ion analysis in snowpacks suggests that sea spray, mineral dust, and combustion aerosol are all relevant to the fate of PFAS in the Lake Hazen watershed. Distinct drifts of light and dark snow (enriched with light absorbing particles, LAPs) facilitate the study of particle loads on the fate of PFAS in the snowpack. Total PFAS (ΣPFAS, ng m-2) loads are lower in snowpacks enriched with LAPs and are attributed to reductions in snowpack albedo combined with enhanced post-depositional melting. Elevated concentrations of PFCA are observed in the top 5 m of the water column during snowmelt periods compared to ice-covered or ice-free periods. PFAS concentrations in deep waters of the Lake Hazen water column were consistent between snowmelt, ice-free, and ice-covered periods, which is ascribed to the delivery of dense and turbid glacier meltwaters mixing PFAS throughout the Lake Hazen water column. These observations highlight the underlying mechanisms in PFAS cycling in High Arctic Lakes particularly in the context of increased particle loads and melting.

Atmospheric Concentrations and Wet/Dry Loadings of Mercury at the Remote Experimental Lakes Area, Northwestern Ontario, Canada.

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.

400-Year Record of Atmospheric Mercury from Tree-Rings in Northwestern Canada.

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.

Sources of Methylmercury to Snowpacks of the Alberta Oil Sands Region: A Study of In Situ Methylation and Particulates.

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 loadings decreased exponentially over this same distance (R2 = 0.49, p = 0.0002; R2 = 0.56, p < 0.0001). Thus, at near-field sites, total MeHg loadings in snowpacks were high due to high particle loadings, even though particles originating from industrial activities were not MeHg rich compared to those at remote sites. More research is required to identify the industrial sources of snowpack particles in the AOSR.

Determination of monomethylmercury and dimethylmercury in the Arctic marine boundary layer.

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.

Atmospheric deposition of mercury and methylmercury to landscapes and waterbodies of the Athabasca oil sands region.

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, p < 0.01) 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.

Mercury deposition to lake sediments near historic gold mines in northern Canada.

Mercury (Hg) contamination in aquatic systems can lead to adverse human and environmental health outcomes. Yellowknife, a city in Canada's Northwest Territories, is a historic mining community, with two large gold mines (Giant Mine and Con Mine) that used Hg amalgamation methods to extract gold between ∼1938 and 1960. We analyzed dated sediment cores from 20 small lakes to investigate the spatial and temporal Hg deposition patterns within 50 km of Giant Mine. Breakpoint analysis of the within-lake z-score normalized anthropogenic Hg flux indicates two significant time periods of changing emission rates. The first is a significant increase in Hg deposition rate (∼1925) during the time of gold exploration in the region and onset of Hg amalgamation (1938) and the second is a significant decrease in deposition rate that begins around the time of the cessation of Hg amalgamation at Giant Mine (∼1959). Sediment Hg concentrations exceeded the Canadian Council for Ministers of the Environment Interim Sediment Quality Guideline (ISQG) for Hg (0.17 mg/kg dw) in 55% of the lakes (n = 11) during mining (1948-1999). All lakes within 5 km of the Giant Mine roaster stack exceeded CCME ISQG during mining (n = 8), with a 4-fold increase in total Hg concentration observed during mining at these near-field (<5 km from stack) sites. We observed evidence of enriched Hg in near-field, mid-field, and far-field sites. The elevated sedimentary Hg concentrations during mining in near-field sites would have posed a hazard to human and wildlife health during the height of emissions, however the significant decrease in Hg concentrations since the closure of mines in the region demonstrate the potential for recovery in these aquatic ecosystems.

A 50 year record for perfluoroalkyl acids in the high arctic: implications for global and local transport.

Perfluoroalkyl acids (PFAAs) are persistent compounds that are ubiquitous globally, though some uncertainties remain in the understanding of their long-range transport mechanisms. They are frequently detected in remote locations, where local sources may be unimportant. We collected a 16.5 metre ice core on northern Ellesmere Island, Nunavut, Canada to investigate PFAA deposition trends and transport mechanisms. The dated core represents fifty years of deposition (1967-2016), which accounts for the longest deposition record of perfluoroalkylcarboxylic acids (PFCAs) in the Arctic and the longest record of perfluoroalkylsulfonic acids (PFSAs) globally. PFCAs were detected frequently after the 1990s and have been increasing since. Homologue pair correlations, molar concentration ratios, and model comparisons suggest that PFCAs are primarily formed through oxidation of volatile precursors. PFSAs showed no discernible trend, with concentrations at least an order of magnitude lower than PFCAs. We observed episodic deposition of some PFAAs, notably perfluorooctane sulfonic acid (PFOS) and perfluorobutane sulfonic acid (PFBS) before the 1990s, which may be linked to Arctic military activities. Tracer analysis suggests that marine aerosols and mineral dust are relevant as transport vectors for selected PFAAs during specific time periods. These observations highlight the complex mechanisms responsible for the transport and deposition of PFAAs in the High Arctic.

Mercury at the top of the world: A 31-year record of mercury in Arctic char in the largest High Arctic lake, linked to atmospheric mercury concentrations and climate oscillations.

Lake Hazen, the largest lake north of the Arctic circle, is being impacted by mercury (Hg) pollution and climate change. The lake is inhabited by two morphotypes of land-locked Arctic char (Salvelinus alpinus), a sensitive indicator species for pollution and climatic impacts. The objectives of this study were to describe the trends in Hg concentration over time and to determine the relationship of climate to length-at-age and Hg concentrations in each char morphotype, as well as the relationship to atmospheric Hg measurements at a nearby monitoring station. Results for Hg in char muscle were available from 20 sampling years over the period 1990 to 2021. We found significant declines in Hg concentrations for both morphotypes during the 31-year study period. Increased rain and earlier freeze-up of lake ice during the summer growing season was linked to increased length-at-age in both char morphotypes. For the large morphotype, higher total gaseous Hg in the fall and winter seasons was related to higher concentrations of Hg in char, while increased glacial runoff was related to decreases in char Hg. For the small morphotype char, increased snow and snow accumulation in the fall season were linked to declines in char Hg concentration. The Atlantic Multidecadal Oscillation and Arctic Oscillation were positively related to the large char Hg trend and Arctic Oscillation was positively related to the small char Hg trend. Significant trend relationships between atmospheric Hg and Hg in biota in remote regions are rare and uniquely valuable for evaluation of the effectiveness of the Minamata Convention and related monitoring efforts.

Canadian high arctic ice core records of organophosphate flame retardants and plasticizers.

Organophosphate esters (OPEs) have been used as flame retardants, plasticizers, and anti-foaming agents over the past several decades. Of particular interest is the long range transport potential of OPEs given their ubiquitous detection in Arctic marine air. Here we report 19 OPE congeners in ice cores drilled on remote icefields and ice caps in the Canadian high Arctic. A multi-decadal temporal profile was constructed in the sectioned ice cores representing a time scale spanning the 1970s to 2014-16. In the Devon Ice Cap record, the annual total OPE (∑OPEs) depositional flux for all of 2014 was 81 µg m-2, with the profile dominated by triphenylphosphate (TPP, 9.4 µg m-2) and tris(2-chloroisopropyl) phosphate (TCPP, 42 µg m-2). Here, many OPEs displayed an exponentially increasing depositional flux including TCPP which had a doubling time of 4.1 ± 0.44 years. At the more northern site on Mt. Oxford icefield, the OPE fluxes were lower. Here, the annual ∑OPEs flux in 2016 was 5.3 µg m-2, dominated by TCPP (1.5 µg m-2) but also tris(2-butoxyethyl) phosphate (1.5 µg m-2 TBOEP). The temporal trend for halogenated OPEs in the Mt. Oxford icefield is bell-shaped, peaking in the mid-2000s. The observation of OPEs in remote Arctic ice cores demonstrates the cryosphere as a repository for these substances, and supports the potential for long-range transport of OPEs, likely associated with aerosol transport.

Methylmercury cycling in High Arctic wetland ponds: controls on sedimentary production.

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.

Methylmercury cycling in High Arctic wetland ponds: sources and sinks.

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.

Mercury in Arctic marine ecosystems: sources, pathways and exposure.

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.

Investigation of perfluoroalkyl substances in proglacial rivers and permafrost seep in a high Arctic watershed.

We measured perfluoroalkyl substances (PFAS) in proglacial rivers and along a non-glacial freshwater continuum to investigate the role of snow and ice melting in their transport and fate within the Lake Hazen watershed (82° N). PFAS concentrations in glacial rivers were higher than those in surface waters of Lake Hazen, suggesting melting glacial ice increased PFAS concentrations in the lake. Stream water derived from subsurface soils along a non-glacial (permafrost thaw and snowmelt) freshwater continuum was a source of PFAS to Lake Hazen. Lower concentrations were found downstream of a meadow wetland relative to upstream locations along the continuum, suggesting PFAS partitioning into vegetation and soil as water flowed downstream towards Lake Hazen. Our estimations indicate that total PFAS inputs from glacial rivers and snowmelt were 1.6 kg (78%) and 0.44 kg (22%), respectively, into Lake Hazen, totalling 2.04 kg, and the output of PFAS from Lake Hazen was 0.64 kg. A positive net annual change of 1.4 kg indicates PFAS had notable residence times and/or net storage in Lake Hazen.

Influence of forest canopies on the deposition of methylmercury to boreal ecosystem watersheds.

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.