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.

AQUA-GAPS/MONET-Derived Concentrations and Trends of PAHs and Polycyclic Musks across Global Waters.

Polycyclic aromatic hydrocarbons (PAHs), released from petrogenic, pyrogenic or diagenetic sources (degradation of wood materials), are of global concern due to their adverse effects, and potential for long-range transport. While dissolved PAHs have been frequently reported in the literature, there has been no consistent approach of sampling across water bodies. Passive samplers from the AQUA/GAPS-MONET initiative were deployed at 46 sites (28 marine and 18 freshwater), and analyzed for 28 PAHs and six polycyclic musks (PCMs) centrally. Freely dissolved PAH concentrations were dominated by phenanthrene (mean concentration 1500 pg L-1; median 530 pg L-1) and other low molecular weight compounds. Greatest concentrations of phenanthrene, fluoranthene, and pyrene were typically from the same sites, mostly in Europe and North America. Of the PCMs, only galaxolide (72% of samples) and tonalide (61%) were regularly detected, and were significantly cross-correlated. Benchmarking of PAHs relative to penta- and hexachlorobenzene confirmed that the most remote sites (Arctic, Antarctic, and mountain lakes) displayed below average PAH concentrations. Concentrations of 11 of 28 PAHs, galaxolide and tonalide were positively correlated (P < 0.05) with population density within a radius of 5 km of the sampling site. Characteristic PAH ratios gave conflicting results, likely reflecting multiple PAH sources and postemission changes.

Distribution and trophodynamics of substituted diphenylamine antioxidants and benzotriazole UV stabilizers in a freshwater ecosystem and the adjacent riparian environment.

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are industrial additives of emerging environmental concern. However, little is known about their environmental fate and bioaccumulation. This study investigated the concentrations of SDPAs and BZT-UVs in the water, sediment and biota samples in the freshwater ecosystem and adjacent riparian environment using Hamilton Harbour in the Great Lakes of North America as a study site. The bioaccumulation factors and trophodynamics of these contaminants were studied using field-collected samples. Eight target SDPAs and two BZT-UVs (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234) and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328)) were frequently detected in the sediment, water and biota samples. UV328 showed significantly greater concentrations in water (0.28-2.8 ng L-1) and sediment (8.3-48 ng g-1, dry weight) than other target contaminants, implying greater contamination of UV328 in Hamilton Harbour. SDPAs exhibited trophic dilution in species living in the water, whereas UV234 was biomagnified in the same samples. No clear trophodynamic trend was found for UV328 for water-respiring species. Air-breathing invertebrates had higher concentrations of both SDPAs and BZT-UVs than water-respiring invertebrates, and biomagnification was observed particularly for adult dragonflies. These results suggest that the trophodynamics of SDPAs and BZT-UVs vary depending on whether the food web is terrestrial or aquatic. Future research should investigate the occurrence and partitioning of SDPAs and BZT-UVs in the air-water interface and evaluate the toxicities of these contaminants in air-breathing species.

Investigation of the Link between Per- and Polyfluoroalkyl Substances and Stress Biomarkers in Bottlenose Dolphins (Tursiops truncatus).

Bottlenose dolphins (Tursiops truncatus) are keystone and sentinel species in the world's oceans. We studied correlations between per- and polyfluoroalkyl substances (PFAS) and their stress axis. We investigated associations between plasma biomarkers of 12 different PFAS variants and three cortisol pools (total, bound, and free) in wild T. truncatus from estuarine waters of Charleston, South Carolina (n = 115) and Indian River Lagoon, Florida (n = 178) from 2003 to 2006, 2010-2013, and 2015. All PFAS and total cortisol levels for these dolphins were previously reported; bound cortisol levels and free cortisol calculations have not been previously reported. We tested null hypotheses that levels of each PFAS were not correlated with those of each cortisol pool. Free cortisol levels were lower when PFOS, PFOA, and PFHxS biomarker levels were higher, but free cortisol levels were higher when PFTriA was higher. Bound cortisol levels were higher when there were higher PFDA, PFDoDA, PFDS, PFTeA, and PFUnDA biomarkers. Total cortisol was higher when PFOA was lower, but total cortisol was higher when PFDA, PFDoDA, PFTeA, and PFTriA were higher. Additional analyses indicated sex and age trends, as well as heterogeneity of effects from the covariates carbon chain length and PFAS class. Although this is a cross-sectional observational study and, therefore, could reflect cortisol impacts on PFAS toxicokinetics, these correlations are suggestive that PFAS impacts the stress axis in T. truncatus. However, if PFAS do impact the stress axis of dolphins, it is specific to the chemical structure, and could affect the individual pools of cortisol differently. It is critical to conduct long-term studies on these dolphins and to compare them to populations that have no or little expose to PFAS.

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.

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.

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.

Divergent Temporal Trends of Mercury in Arctic Char from Paired Lakes Influenced by Climate-Related Drivers.

Climate-driven changes including rising air temperatures, enhanced permafrost degradation, and altered precipitation patterns can have profound effects on contaminants, such as mercury (Hg), in High Arctic lakes. Two physically similar lakes, East Lake and West Lake at the Cape Bounty Arctic Watershed Observatory on Melville Island, Nunavut, Canada are being affected by climate change differently. Both lakes have experienced permafrost degradation in their catchments; however, West Lake has also undergone multiple underwater Mass Movement Events (MMEs; beginning in fall 2008), leading to a sustained 50-fold increase in turbidity. This provided the unique opportunity to understand the potential impacts of permafrost degradation and other climate-related effects on Hg concentrations and body condition of landlocked Arctic char (Salvelinus alpinus), an important sentinel species across the Circum-Arctic. Our objectives were to assess temporal trends in char Hg concentrations and to determine potential mechanisms driving the trends. There was a significant decrease in Hg concentrations in East Lake char, averaging 6.5%/year and 3.8%/year for length-adjusted and age-adjusted means, respectively, from 2008 to 2019. Conversely, in West Lake there was a significant increase, averaging 7.9%/year and 8.0%/year for length-adjusted and age-adjusted mean Hg concentrations, respectively, for 2009 to 2017 (the last year with sufficient sample size). The best predictors of length-adjusted Hg concentrations in West Lake were carbon and nitrogen stable isotope ratios, indicating a shift in diet including possible dietary starvation brought on by the profound increase in lake turbidity. Our study provides an example of how increasing lake turbidity, a likely consequence of climate warming in Arctic lakes, may influence fish condition and Hg concentrations. Environ Toxicol Chem 2023;42:2712-2725. © 2023 His Majesty the King in Right of Canada and The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

How Many Chemicals in Commerce Have Been Analyzed in Environmental Media? A 50 Year Bibliometric Analysis.

Over the past 50 years, there has been a tremendous expansion in the measurement of chemical contaminants in environmental media. But how many chemicals have actually been determined, and do they represent a significant fraction of substances in commerce or of chemicals of concern? To address these questions, we conducted a bibliometric survey to identify what individual chemicals have been determined in environmental media and their trends over the past 50 years. The CAplus database of CAS, a Division of the American Chemical Society, was searched for indexing roles "analytical study" and "pollutant" yielding a final list of 19,776 CAS Registry Numbers (CASRNs). That list was then used to link the CASRNs to biological studies, yielding a data set of 9.251 × 106 total counts of the CASRNs over a 55 year period. About 14,150 CASRNs were substances on various priority lists or their close analogs and transformation products. The top 100 most reported CASRNs accounted for 34% of the data set, confirming previous studies showing a significant bias toward repeated measurements of the same substances due to regulatory needs and the challenges of determining new, previously unmeasured, compounds. Substances listed in the industrial chemical inventories of Europe, China, and the United States accounted for only about 5% of measured substances. However, pharmaceuticals and current use pesticides were widely measured accounting for 50-60% of total CASRN counts for the period 2000-2015.

Target and Nontarget Screening of Organic Chemicals and Metals in Recycled Plastic Materials.

Increased demand for recycling plastic has prompted concerns regarding potential introduction of hazardous chemicals into recycled goods. We present a broad screening of chemicals in 21 plastic flake and pellet samples from Canadian recycling companies. From target analysis, the organophosphorus ester flame retardants and plasticizers exhibited the highest detection frequencies (DFs) (5-100%) and concentrations (280 chemicals were detected in recycled plastic pellets and flakes, suggesting potential incorporation into recycled goods. Individual concentrations indicate unintentional trace contamination following European Union threshold limits for recycled granules (500 mg/kg) and waste plastic flakes (1,000 mg/kg), although do not reflect toxicological thresholds, if any. Our study highlights that while recycling addresses sustainability goals, additional screening of goods and products made from recycled plastics is needed to fully document potentially hazardous chemicals and exposure.

No accumulation of microplastics detected in western Canadian ringed seals (Pusa hispida).

Ringed seals (Pusa hispida) play a crucial role in Arctic food webs as important pelagic predators and represent an essential component of Inuvialuit culture and food security. Plastic pollution is recognized as a global threat of concern, and Arctic regions may act as sinks for anthropogenic debris. To date, mixed evidence exists concerning the propensity for Canadian Arctic marine mammals to ingest and retain plastic. Our study builds on existing literature by offering the first assessment of plastic ingestion in ringed seals harvested in the western Canadian Arctic. We detected no evidence of microplastic (particles ≥80 µm) retention in the stomachs of ten ringed seals from the Inuvialuit Settlement Region (ISR) in the Northwest Territories, Canada. These results are consistent with previous studies that have found that some marine mammals do not accumulate microplastics in evaluated regions.

Modeling historical budget for ß-Hexachlorocyclohexane (HCH) in the Arctic Ocean: A contrast to α-HCH.

The historical annual loading to, removal from, and cumulative burden in the Arctic Ocean for ß-hexachlorocyclohexane (ß-HCH), an isomer comprising 5-12% of technical HCH, is investigated using a mass balance box model from 1945 to 2020. Over the 76 years, loading occurred predominantly through ocean currents and river inflow (83%) and only a small portion via atmospheric transport (16%). ß-HCH started to accumulate in the Arctic Ocean in the late 1940s, reached a peak of 810 t in 1986, and decreased to 87 t in 2020, when its concentrations in the Arctic water and air were ∼30 ng m-3 and ∼0.02 pg m-3, respectively. Even though ß-HCH and α-HCH (60-70% of technical HCH) are both the isomers of HCHs with almost identical temporal and spatial emission patterns, these two chemicals have shown different major pathways entering the Arctic. Different from α-HCH with the long-range atmospheric transport (LRAT) as its major transport pathway, ß-HCH reached the Arctic mainly through long-range oceanic transport (LROT). The much higher tendency of ß-HCH to partition into the water, mainly due to its much lower Henry's Law Constant than α-HCH, produced an exceptionally strong pathway divergence with ß-HCH favoring slow transport in water and α-HCH favoring rapid transport in air. The concentration and burden of ß-HCH in the Arctic Ocean are also predicted for the year 2050 when only 4.4-5.3 t will remain in the Arctic Ocean under the influence of climate change.

Influences of climate change on long-term time series of persistent organic pollutants (POPs) in Arctic and Antarctic biota.

Time series of contaminants in the Arctic are an important instrument to detect emerging issues and to monitor the effectiveness of chemicals regulation, based on the assumption of a direct reflection of changes in primary emissions. Climate change has the potential to influence these time trends, through direct physical and chemical processes and/or changes in ecosystems. This study was part of an assessment of the Arctic Monitoring and Assessment Programme (AMAP), analysing potential links between changes in climate-related physical and biological variables and time trends of persistent organic pollutants (POPs) in Arctic biota, with some additional information from the Antarctic. Several correlative relationships were identified between POP temporal trends in freshwater and marine biota and physical climate parameters such as oscillation indices, sea-ice coverage, temperature and precipitation, although the mechanisms behind these observations remain poorly understood. Biological data indicate changes in the diet and trophic level of some species, especially seabirds and polar bears, with consequences for their POP exposure. Studies from the Antarctic highlight increased POP availability after iceberg calving. Including physical and/or biological parameters in the POP time trend analysis has led to small deviations in some declining trends, but did generally not change the overall direction of the trend. In addition, regional and temporary perturbations occurred. Effects on POP time trends appear to have been more pronounced in recent years and to show time lags, suggesting that climate-related effects on the long time series might be gaining importance.

Feeding and contaminant patterns of sub-arctic and arctic ringed seals: Potential insight into climate change-contaminant interactions.

To provide insight into how climate-driven diet shifts may impact contaminant exposures of Arctic species, we compared feeding ecology and contaminant concentrations in ringed seals (Pusa hispida) from two Canadian sub-Arctic (Nain at 56.5°N, Arviat at 61.1°N) and two Arctic sites (Sachs Harbour at 72.0 °N, Resolute Bay at 74.7 °N). In the sub-Arctic, empirical evidence of changing prey fish communities has been documented, while less community change has been reported in the Arctic to date, suggesting current sub-Arctic conditions may be a harbinger of future Arctic conditions. Here, Indigenous partners collected tissues from subsistence-harvested ringed seals in 2018. Blubber fatty acids (FAs) and muscle stable isotopes (δ15N, δ13C) indicated dietary patterns, while measured contaminants included heavy metals (e.g., total mercury (THg)), legacy persistent organic pollutants (e.g., dichlorodiphenyltrichloroethanes (DDTs)), polybrominated diphenyl ethers (PBDEs), and per-/polyfluoroalkyl substances (PFASs). FA signatures are distinct between sub-Arctic and Resolute Bay seals, likely related to higher consumption of southern prey species including capelin (Mallotus villosus) in the sub-Arctic but on-going feeding on Arctic species in Resolute Bay. Sachs Harbour ringed seals show FA overlap with all locations, possibly consuming both southern and endemic Arctic species. Negative δ13C estimates for PFAS models suggest that more pelagic, sub-Arctic type prey (e.g., capelin) increases PFAS concentrations, whereas the reverse occurs for, e.g., THg, ΣPBDE, and ΣDDT. Inconsistent directionality of δ15N estimates in the models likely reflects baseline isotopic variation not trophic position differences. Adjusting for the influence of diet suggests that if Arctic ringed seal diets become more like sub-Arctic seals due to climate change, diet-driven increases may occur for newer contaminants like PFASs, but not for more legacy contaminants. Nonetheless, temporal trends studies are still needed, as are investigations into the potential confounding influence of baseline isotope variation in spatial studies of contaminants in Arctic biota.

Gas Chromatography-(Cyclic) Ion Mobility Mass Spectrometry: A Novel Platform for the Discovery of Unknown Per-/Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFASs) have been widely used since the 1940s in industry and everyday household products. They also persist in the environment and bioaccumulate in humans and wildlife. Despite these concerns, the identities of most PFASs in environmental and biological samples are unknown. Herein, we describe a novel cyclic ion mobility mass spectrometer (cIMS), hyphenated with gas chromatography (GC) atmospheric pressure chemical ionization, that can reveal the presence of unknown PFASs on the basis of the ratio of their mass and collision cross section (CCS). Prediction of the CCS of ca. 20,000 chemicals used in industry and commerce indicates that most compounds characterized by CCS values that are less than the sum of 100 Å2 and one-fifth of their mass are either PFASs or polybrominated flame retardants. When this filter is applied to GC-cIMS data collected from a set of 20 indoor dust samples, PFAS compounds are revealed without prior knowledge of their occurrence. Validation of this approach was performed using SRM 2585, a standard reference material of household dust, by comparing the PFASs detected with those (tentatively) identified in previous studies. Chlorofluoro phthalimides tentatively identified previously were confirmed with a synthesized standard. The method also reveals the presence of chlorofluoro n-alkanes as an emerging class of "forever chemicals" that contaminate the indoor environment.

Temporal trends of mercury in Arctic biota: 10 more years of progress in Arctic monitoring.

Temporal trend analysis of (total) mercury (THg) concentrations in Arctic biota were assessed as part of the 2021 Arctic Monitoring and Assessment Programme (AMAP) Mercury Assessment. A mixed model including an evaluation of non-linear trends was applied to 110 time series of THg concentrations from Arctic and Subarctic biota. Temporal trends were calculated for full time series (6-46 years) and evaluated with a particular focus on recent trends over the last 20 years. Three policy-relevant questions were addressed: (1) What time series for THg concentrations in Arctic biota are currently available? (2) Are THg concentrations changing over time in biota from the Arctic? (3) Are there spatial patterns in THg trends in biota from the Arctic? Few geographical patterns of recent trends in THg concentrations were observed; however, those in marine mammals tended to be increasing at more easterly longitudes, and those of seabirds tended to be increasing in the Northeast Atlantic; these should be interpreted with caution as geographic coverage remains variable. Trends of THg in freshwater fish were equally increasing and decreasing or non-significant while those in marine fish and mussels were non-significant or increasing. The statistical power to detect trends was greatly improved compared to the 2011 AMAP Mercury Assessment; 70% of the time series could detect a 5% annual change at the 5% significance level with power ≥ 80%, while in 2011 only 19% met these criteria. Extending existing time series, and availability of new, powerful time series contributed to these improvements, highlighting the need for annual monitoring, particularly given the spatial and temporal information needed to support initiatives such as the Minamata Convention on Mercury. Collecting the same species/tissues across different locations is recommended. Extended time series from Alaska and new data from Russia are also needed to better establish circumarctic patterns of temporal trends.

Mercury Isotope Variations in Lake Sediment Cores in Response to Direct Mercury Emissions from Non-Ferrous Metal Smelters and Legacy Mercury Remobilization.

Nature archives record atmospheric mercury (Hg) depositions from directly emitted Hg and re-emitted legacy Hg. Tracing the legacy versus newly deposited Hg is still, however, challenging. Here, we measured Hg isotope compositions in three dated sediment cores at different distances from the Flin Flon smelter, the largest Canadian Hg sources to the atmosphere during the 1930s-2000s. During the smelter's operative period, Hg isotope compositions showed limited variations in the near-field lake (<10 km) sediments but were rather variable in middle- (20-75 km) and far-field lake (∼800 km) sediments. Only the post-2000 sediments in middle/far-field lakes showed significantly negative Hg isotope shifts, while sediments from the 1970s-1990s had Hg isotope values resembling those of near-field lake post-1930 sediments. We suggest that the smelter's peak Hg emissions during the 1970s-1990s, which coincided with the deployment of a super stack in the mid-1970s, largely increased the long-range dispersion of smelter plumes. For the top post-2000 sediments, the fugitive dust from ore tailings and terrestrial legacy Hg re-emissions dominated Hg deposition in near-field lakes and middle/far-field lakes, respectively. Our study demonstrates that legacy Hg remobilization now exports substantial amounts of Hg to ecosystems, highlighting the need for aggressive remediation measures of Hg-contaminated sites.

Climate change and mercury in the Arctic: Biotic interactions.

Global climate change has led to profound alterations of the Arctic environment and ecosystems, with potential secondary effects on mercury (Hg) within Arctic biota. This review presents the current scientific evidence for impacts of direct physical climate change and indirect ecosystem change on Hg exposure and accumulation in Arctic terrestrial, freshwater, and marine organisms. As the marine environment is elevated in Hg compared to the terrestrial environment, terrestrial herbivores that now exploit coastal/marine foods when terrestrial plants are iced over may be exposed to higher Hg concentrations. Conversely, certain populations of predators, including Arctic foxes and polar bears, have shown lower Hg concentrations related to reduced sea ice-based foraging and increased land-based foraging. How climate change influences Hg in Arctic freshwater fishes is not clear, but for lacustrine populations it may depend on lake-specific conditions, including interrelated alterations in lake ice duration, turbidity, food web length and energy sources (benthic to pelagic), and growth dilution. In several marine mammal and seabird species, tissue Hg concentrations have shown correlations with climate and weather variables, including climate oscillation indices and sea ice trends; these findings suggest that wind, precipitation, and cryosphere changes that alter Hg transport and deposition are impacting Hg concentrations in Arctic marine organisms. Ecological changes, including northward range shifts of sub-Arctic species and altered body condition, have also been shown to affect Hg levels in some populations of Arctic marine species. Given the limited number of populations and species studied to date, especially within Arctic terrestrial and freshwater systems, further research is needed on climate-driven processes influencing Hg concentrations in Arctic ecosystems and their net effects. Long-term pan-Arctic monitoring programs should consider ancillary datasets on climate, weather, organism ecology and physiology to improve interpretation of spatial variation and time trends of Hg in Arctic biota.

Climate change influence on the levels and trends of persistent organic pollutants (POPs) and chemicals of emerging Arctic concern (CEACs) in the Arctic physical environment - a review.

Climate change brings about significant changes in the physical environment in the Arctic. Increasing temperatures, sea ice retreat, slumping permafrost, changing sea ice regimes, glacial loss and changes in precipitation patterns can all affect how contaminants distribute within the Arctic environment and subsequently impact the Arctic ecosystems. In this review, we summarized observed evidence of the influence of climate change on contaminant circulation and transport among various Arctic environment media, including air, ice, snow, permafrost, fresh water and the marine environment. We have also drawn on parallel examples observed in Antarctica and the Tibetan Plateau, to broaden the discussion on how climate change may influence contaminant fate in similar cold-climate ecosystems. Significant knowledge gaps on indirect effects of climate change on contaminants in the Arctic environment, including those of extreme weather events, increase in forests fires, and enhanced human activities leading to new local contaminant emissions, have been identified. Enhanced mobilization of contaminants to marine and freshwater ecosystems has been observed as a result of climate change, but better linkages need to be made between these observed effects with subsequent exposure and accumulation of contaminants in biota. Emerging issues include those of Arctic contamination by microplastics and higher molecular weight halogenated natural products (hHNPs) and the implications of such contamination in a changing Arctic environment is explored.