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The monitoring of legacy contaminants in sentinel northern marine mammals has revealed some of the highest concentrations globally. However, investigations into the presence of chemicals of emerging Arctic concern (CEACs) and other lesser-known chemicals are rarely conducted, if at all. Here, we used a nontarget/suspect approach to screen for thousands of different chemicals, including many CEACs and plastic-related compounds (PRCs) in blubber/adipose from killer whales (Orcinus orca), narwhals (Monodon monoceros), long-finned pilot whales (Globicephala melas), and polar bears (Ursus maritimus) in East Greenland. 138 compounds were tentatively identified mostly as PRCs, and four were confirmed using authentic standards: di(2-ethylhexyl) phthalate (DEHP), diethyl phthalate (DEP), di(2-propylheptyl) phthalate (DPHP), and one antioxidant (Irganox 1010). Three other PRCs, a nonylphenol isomer, 2,6-di-tert-butylphenol, and dioctyl sebacate, exhibited fragmentation patterns matching those in library databases. While phthalates were only above detection limits in some polar bear and narwhal, Irganox 1010, nonylphenol, and 2,6-di-tert-butylphenol were detected in >50% of all samples. This study represents the first application of a nontarget/suspect screening approach in Arctic cetaceans, leading to the identification of multiple PRCs in their blubber. Further nontarget analyses are warranted to comprehensively characterize the extent of CEAC and PRC contamination within Arctic marine food webs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The historical contamination of eastern Canadian shelf waters remains an ongoing concern, predominantly stemming from anthropogenic discharges in the Great Lakes region. Although legacy persistent organic pollutants (POPs) were banned decades ago, it remains unclear whether their concentrations have sufficiently decreased to safer levels in cetaceans that feed in the continental shelf waters of the northwestern Atlantic. This study compares polychlorinated biphenyl (PCB) and organochlorine pesticide (OC) accumulation in six cetacean species sampled in the Northwest Atlantic from 2015 to 2022. We assessed the influence of relative trophic level and foraging habitat preferences on POP accumulations among species using stable isotopes and fatty acids as dietary tracers. We further identified the species most susceptible to the effects of these contaminants. Killer whales (Orcinus orca) exhibited the highest PCB (∼100 mg/kg lw) and OC concentrations, followed by other odontocetes, with lowest concentrations in mysticetes. Stable isotope analysis revealed an unexpected lack of correlation between δ 15 N values and contaminant levels. However, there was a positive correlation between δ 13 C values and POP concentrations. Cetaceans foraging on pelagic prey species, as indicated by elevated proportions of the FA markers 22:1n11 and 20:1n9, had lower contaminant loads compared to cetaceans with benthic/coastal FA signatures. PCB and DDT (dichlorodiphenyltrichloroethane) concentrations are lower now in most cetacean species than in the 1980s and 1990s, likely due to regulatory measures restricting their production and use. Although current PCB concentrations for most species are under the thresholds for high risks of immune and reproductive failure, concentrations in killer whales exceed all established toxicity thresholds, underscoring the need for further action to reduce sources of these contaminants to the continental shelf waters of the northwestern Atlantic., Competing Interests: Declaration of competing interest The authors declare no competitng interest., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Flame retardants (FRs) are commonly added to commercial products to achieve flammability resistance. Since most of them are not chemically bonded to the materials, they could be leached to the environment during the production and disposal cycle. These FRs were categorised based on their chemical nature, including brominated, organophosphorus-, mineral- and nitrogen-based. This review summarised the abiotic degradation reactions of these four classes of FRs, with a focus on thermal and photodegradation reactions in environmental and food matrices. Only 24 papers have reported related information on abiotic degradation reactions that could be useful for predicting possible degradation pathways, and most focused on brominated FRs. Most studies also investigated the thermal degradation of FRs under high temperatures (>400 °C), which exceeds the normal cooking temperature at 100-300 °C. For photodegradation, studies have used up to five times the energy typically used in UV radiation during food processing. It is recommended that future studies investigate the fate of these FRs in foods under more realistic processing conditions, to provide a more comprehensive picture of the estimated consumption of FRs and their degradation products from foods, and facilitate a better risk assessment of the use of these novel FRs.

Killer whales (Orcinus orca) historically restricted to certain Arctic regions due to extensive sea ice have recently been documented farther north and for longer durations in the Canadian Arctic. These apex predators accumulate high levels of persistent organic pollutants (POPs). The objective of this study was to evaluate the concentrations and profiles of POPs in killer whales of the Canadian Arctic, thus determining potential risks for Inuit communities if consumed. Biopsies were collected from 33 killer whales across areas of the Canadian Arctic between 2009 and 2021. Significant variability in POP concentrations was observed among whales. The cumulative POP concentrations ranged from 12 to >2270 mg/kg lw, representing ∼200-fold increase from the least to the most contaminated individual. The rank order of concentrations of the top five contaminant classes was ∑DDT, ∑PCB, ∑CHL, ∑Toxaphene, and Dieldrin. Several emerging Arctic contaminants were detected, including chlorpyrifos, endosulfan, pentachloroanisole, and polychlorinated naphthalenes, although at relatively lower concentrations than legacy POPs. Considering the elevated blubber POP levels in killer whales, recommended daily consumption thresholds, established based on human tolerable daily intake (TDI) values, were notably restricted for ∑PCB (<0.14 g), ∑DDT (<6.9 g), ∑CHL (<13 g), dieldrin (<8 g) and heptachlor epoxide (<5 g). Killer whales in the Canadian Arctic exhibited higher POP concentrations than other commonly hunted species such as polar bears, ringed seals, and Arctic char. We acknowledge that a more holistic risk assessment of diet is required to assess the cumulative impacts of contaminant mixtures as well as nutritional quality of tissues commonly consumed by northern communities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

The movement of per- and polyfluoroalkyl substances (PFAS) through linked aquatic-terrestrial food webs is not well understood. Tree swallows ( Tachycineta bicolor ) in such systems may be exposed to PFAS from multiple abiotic and/or biotic compartments. We show from fatty acid signatures and carbon stable isotopes that tree swallow nestlings in southwestern Ontario fed on both terrestrial and aquatic macroinvertebrates. The PFAS profiles of air, terrestrial invertebrates, and swallows were dominated by perfluorooctanesulfonic acid (PFOS). Short-chain perfluoroalkyl acids (PFAAs) were largely restricted to air, surface water, and sediment, and long-chain PFAAs were mainly found in aquatic invertebrates and tree swallows. PFOS, multiple long-chain perfluorocarboxylic acids [perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorotridecanoic acid (PFTrDA)] and perfluorooctane sulfonamide precursors were estimated to bioaccumulate from air to tree swallows. PFOS bioaccumulated from air to terrestrial invertebrates, and PFOS, PFDA, and perfluorooctane sulfonamidoacetic acids (FOSAAs) bioaccumulated from water to aquatic invertebrates. PFOS showed biomagnification from both terrestrial and aquatic invertebrates to tree swallows, and PFDA and FOSAAs were also biomagnified from aquatic invertebrates to tree swallows. The movement of PFAS through aquatic-terrestrial food webs appears congener- and compartment-specific, challenging the understanding of PFAS exposure routes for multiple species involved in these food webs.

Polar bear and toothed whales in the Arctic exhibit orders of magnitude differences in concentrations of legacy persistent organic pollutants (POPs), which may be attributed to comparisons made across regions and different time frames. These interspecific differences could be influenced by variations in biological susceptibility, including differences in xenobiotic biotransformation between polar bear, from the order Carnivora, and toothed whales, from the order Artiodactyla, as well as ecological factors, such as variation in feeding patterns. Here, we analyzed samples from subsistence-harvested toothed whales and polar bear in East Greenland collected between 2012 and 2021 and quantitatively compared interspecific differences in blubber/adipose polychlorinated biphenyl (PCB) and organochlorine (OC) pesticide concentrations. We further determined fatty acid (FA) signatures as dietary tracers to evaluate how feeding patterns influence POP concentrations relative to the influence of biological differences between taxa. Killer whale exhibited the highest mean concentrations of ΣPCBs (57.0 ± 14.0 mg/kg lw), Σdichlorodiphentlytrichloroethanes (ΣDDTs; 55.7 ± 13.1), and Σchlordanes (ΣCHLs; 23.1 ± 5.6 mg/kg lw), while polar bear showed the second highest concentrations for ΣPCBs (12.5 ± 1.3 mg/kg lw), but comparable or even lower levels of all OCs relative to narwhal and pilot whale. Linear models using FA patterns as explanatory variables for POP concentrations demonstrated that, for ΣPCBs, diet differences explained most of the variation. Conversely, biological differences explained more of the variation for most OCs, especially for DDT, for which polar bear showed the lowest concentrations despite feeding on similarly high trophic position prey as killer whale. This novel quantitative comparison confirms that significant differences in legacy POP concentrations occur among Arctic marine mammal predators. Furthermore, the drivers of these differences are contaminant-specific, with feeding patterns primarily influencing PCB concentrations, taxa-specific biological characteristics (e.g., in xenobiotic biotransformation capacity) affecting DDT concentrations, and both factors contributing to variations in other OCs., (Copyright © 2023. Published by Elsevier B.V.)

Lipophilic persistent organic pollutants (POPs) tend to biomagnify in food chains, resulting in higher concentrations in species such as killer whales ( Orcinus orca ) feeding on marine mammals compared to those consuming fish. Advancements in dietary studies include the use of quantitative fatty acid signature analysis (QFASA) and differentiation of feeding habits within and between populations of North Atlantic (NA) killer whales. This comprehensive study assessed the concentrations of legacy and emerging POPs in 162 killer whales from across the NA. We report significantly higher mean levels of polychlorinated biphenyls (PCBs), organochlorine pesticides, and flame retardants in Western NA killer whales compared to those of Eastern NA conspecifics. Mean ∑PCBs ranged from ∼100 mg/kg lipid weight (lw) in the Western NA (Canadian Arctic, Eastern Canada) to ∼50 mg/kg lw in the mid-NA (Greenland, Iceland) to ∼10 mg/kg lw in the Eastern NA (Norway, Faroe Islands). The observed variations in contaminant levels were strongly correlated with diet composition across locations (inferred from QFASA), emphasizing that diet and not environmental variation in contaminant concentrations among locations is crucial in assessing contaminant-associated health risks in killer whales. These findings highlight the urgency for implementing enhanced measures to safely dispose of POP-contaminated waste, prevent further environmental contamination, and mitigate the release of newer and potentially harmful contaminants.

Combining mercury and stable isotope data sets of consumers facilitates the quantification of whether contaminant variation in predators is due to diet, habitat use and/or environmental factors. We investigated inter-species variation in total Hg (THg) concentrations, trophic magnification slope between δ 15 N and THg, and relationships of THg with δ 13 C and δ 34 S in 15 fish and four marine mammal species (249 individuals in total) in coastal Arctic waters. Median THg concentration in muscle varied between species ranging from 0.08 ± 0.04 μg g -1 dw in capelin to 3.10 ± 0.80 μg g -1 dw in beluga whales. Both δ 15 N (r 2  = 0.26) and δ 34 S (r 2  = 0.19) best explained variation in log-THg across consumers. Higher THg concentrations occurred in higher trophic level species that consumed more pelagic-associated prey than consumers that rely on the benthic microbial-based food web. Our study illustrates the importance of using a multi-isotopic approach that includes δ 34 S when investigating trophic Hg dynamics in coastal marine systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Quantifying the diet composition of apex marine predators such as killer whales (Orcinus orca) is critical to assessing their food web impacts. Yet, with few exceptions, the feeding ecology of these apex predators remains poorly understood. Here, we use our newly validated quantitative fatty acid signature analysis (QFASA) approach on nearly 200 killer whales and over 900 potential prey to model their diets across the 5000 km span of the North Atlantic. Diet estimates show that killer whales mainly consume other whales in the western North Atlantic (Canadian Arctic, Eastern Canada), seals in the mid-North Atlantic (Greenland), and fish in the eastern North Atlantic (Iceland, Faroe Islands, Norway). Nonetheless, diet estimates also varied widely among individuals within most regions. This level of inter-individual feeding variation should be considered for future ecological studies focusing on killer whales in the North Atlantic and other oceans. These estimates reveal remarkable population- and individual-level variation in the trophic ecology of these killer whales, which can help to assess how their predation impacts community and ecosystem dynamics in changing North Atlantic marine ecosystems. This new approach provides researchers with an invaluable tool to study the feeding ecology of oceanic top predators., (© 2023 The Authors. Journal of Animal Ecology published by John Wiley & Sons Ltd on behalf of British Ecological Society.)

Perfluoroalkyl acids (PFAAs) include perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorodecane sulfonic acid (PFDS), as well as increasingly used alternative short-chain perfluorosulfonic acids (PFSAs) and short- and long-chain (≥C 9 ) perfluorocarboxylic acids (PFCAs). In the present study, tissues of tree swallows (Tachycineta bicolor) from two sites in southern Ontario, Canada, were analyzed for 17 individual PFAAs and showed egg and nestling tissue (liver, carcass) profiles dominated by PFOS (57-66%). The remaining PFAAs contributed ≤7% each, although collectively the long-chain PFCAs comprised 21-29% of the PFAAs. The short-chain PFSAs and PFCAs were among the lowest concentrations, suggesting that despite increased production and use of these alternative PFAAs, they are not accumulated to the same extent as the long-chain PFSAs and PFCAs. PFOS, PFDS, and some long-chain PFCAs were significantly higher in eggs than in livers and carcasses, whereas PFOA and the two short-chain PFCAs were significantly higher in nestling tissues than in eggs. For the two short-chain PFSAs, concentrations were similar among tissues. Tree swallow tissues at the site near a wastewater treatment plant (WWTP) outfall showed higher concentrations of PFOS, PFDS, PFHxS, and some long-chain PFCAs than tree swallows sampled at the nearby reference site; however, the influence of the WWTP was more equivocal for PFOA, other long-chain PFCAs, and short-chain PFSAs and PFCAs. Carbon stable isotopes (δ 13 C) and fatty acid signatures indicated that the diets of the WWTP swallows were more terrestrial than the reference swallows. Nonetheless, models considering environmental and ecological variables indicated that site was often the primary driver of PFAA variation among the swallows, with less or no influence of dietary patterns, or sex or body condition, revealing that of WWTP effluent can be an important environmental source of the major PFAAs in tree swallows., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

The monitoring of legacy persistent organic pollutants (POPs) in blubber of key sentinel marine mammal species has been conducted using established techniques for decades. Although these methods for polychlorinated biphenyl (PCB) and organochlorine (OC) pesticide determination provide accurate and reproducible results, they possess some drawbacks in terms of cost, time, and a need for large volumes of toxic solvents. QuEChERS (quick, easy, cheap, effective, rugged, and safe) extractions may help address these issues, but have not been applied to marine mammal blubber/adipose. As such, our aim was to develop, validate, and apply a QuEChERS method for the extraction of PCB and OC contaminants in marine mammal blubber. First, we tested multiple solid-phase extraction and clean-up steps to find the approach that provided the cleanest extracts along with consistent and acceptable analyte recovery, accuracy, and precision. QuEChERS extractions followed by two enhanced matrix removal-lipid (EMR-lipid), one primary-secondary amine (PSA), and one silica gel clean-up showed the highest matrix removal and acceptable recoveries of spiked internal (62-97%) and external standards (61-94%). Solvent usage was reduced by ∼393% and extraction time was reduced by ∼25% (from 16 to 12 h). Next, the method was validated using standard reference material (SRM) NIST 1945. Recovery experiments on SRM (n = 5) showed acceptable recovery for 76% and 77% of PCBs and OC pesticides, respectively, and high precision for 73% and 69% of PCBs and OCs, respectively. Finally, the method was used on a set of southeast Greenland killer whales (n = 13), with previously published PCB and OC data. Bland-Altman plots indicated good agreement between QuEChERS and current-use methods for ΣPCBs and some OCs with no significant constant or proportional bias. These results demonstrate that this QuEChERS extraction method represents an effective, lower cost alternative to current-use extractions for PCBs and OCs in blubber, and likely other high-lipid samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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 (δ 15 N, δ 13 C) 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 δ 13 C 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 δ 15 N 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This review summarizes current understanding of how climate change-driven physical and ecological processes influence the levels of persistent organic pollutants (POPs) and contaminants of emerging Arctic concern (CEACs) in Arctic biota and food webs. The review also highlights how climate change may interact with other stressors to impact contaminant toxicity, and the utility of modeling and newer research tools in closing knowledge gaps on climate change-contaminant interactions. Permafrost thaw is influencing the concentrations of POPs in freshwater ecosystems. Physical climate parameters, including climate oscillation indices, precipitation, water salinity, sea ice age, and sea ice quality show statistical associations with POPs concentrations in multiple Arctic biota. Northward range-shifting species can act as biovectors for POPs and CEACs into Arctic marine food webs. Shifts in trophic position can alter POPs concentrations in populations of Arctic species. Reductions in body condition are associated with increases in levels of POPs in some biota. Although collectively understudied, multiple stressors, including contaminants and climate change, may act to cumulatively impact some populations of Arctic biota. Models are useful for predicting the net result of various contrasting climate-driven processes on POP and CEAC exposures; however, for some parameters, especially food web changes, insufficient data exists with which to populate such models. In addition to the impact of global regulations on POP levels in Arctic biota, this review demonstrates that there are various direct and indirect mechanisms by which climate change can influence contaminant exposure, accumulation, and effects; therefore, it is important to attribute POP variations to the actual contributing factors to inform future regulations and policies. To do so, a broad range of habitats, species, and processes must be considered for a thorough understanding and interpretation of the consequences to the distribution, accumulation, and effects of environmental contaminants. Given the complex interactions between climate change, contaminants, and ecosystems, it is important to plan for long-term, integrated pan-Arctic monitoring of key biota and ecosystems, and to collect ancillary data, including information on climate-related parameters, local meteorology, ecology, and physiology, and when possible, behavior, when carrying out research on POPs and CEACs in biota and food webs of the Arctic.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Dramatic environmental shifts are occuring throughout the Arctic from climate change, with consequences for the cycling of mercury (Hg). This review summarizes the latest science on how climate change is influencing Hg transport and biogeochemical cycling in Arctic terrestrial, freshwater and marine ecosystems. As environmental changes in the Arctic continue to accelerate, a clearer picture is emerging of the profound shifts in the climate and cryosphere, and their connections to Hg cycling. Modeling results suggest climate influences seasonal and interannual variability of atmospheric Hg deposition. The clearest evidence of current climate change effects is for Hg transport from terrestrial catchments, where widespread permafrost thaw, glacier melt and coastal erosion are increasing the export of Hg to downstream environments. Recent estimates suggest Arctic permafrost is a large global reservoir of Hg, which is vulnerable to degradation with climate warming, although the fate of permafrost soil Hg is unclear. The increasing development of thermokarst features, the formation and expansion of thaw lakes, and increased soil erosion in terrestrial landscapes are increasing river transport of particulate-bound Hg and altering conditions for aquatic Hg transformations. Greater organic matter transport may also be influencing the downstream transport and fate of Hg. More severe and frequent wildfires within the Arctic and across boreal regions may be contributing to the atmospheric pool of Hg. Climate change influences on Hg biogeochemical cycling remain poorly understood. Seasonal evasion and retention of inorganic Hg may be altered by reduced sea-ice cover and higher chloride content in snow. Experimental evidence indicates warmer temperatures enhance methylmercury production in ocean and lake sediments as well as in tundra soils. Improved geographic coverage of measurements and modeling approaches are needed to better evaluate net effects of climate change and long-term implications for Hg contamination in the Arctic., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Accurate diet estimates are necessary to assess trophic interactions and food web dynamics in ecosystems, particularly for apex predators like cetaceans, which can regulate entire food webs. Quantitative fatty acid analysis (QFASA) has been used to estimate the diets of marine predators in the last decade but has yet to be implemented on free-ranging cetaceans, from which typically only biopsy samples containing outer blubber are available, due to a lack of empirically determined calibration coefficients (CCs) that account for fatty acid (FA) metabolism. Here, we develop and validate QFASA for killer whales using full blubber from managed-care and free-ranging individuals. First, we compute full, inner, and outer blubber CCs from the FA signatures across the blubber layers of managed-care killer whales and their long-term diet items. We then run cross-validating simulations on the managed-care individuals to evaluate the accuracy of diet estimates by comparing full-depth and depth-specific estimates to true diets. Finally, we apply these approaches to subsistence-harvested killer whales from Greenland to test the utility of the method for free-ranging killer whales, particularly for the outer blubber. Accurate diet estimates for the managed-care killer whales were only achieved using killer whale-specific and blubber-layer-specific CCs. Modeled diets for the Greenlandic killer whales largely consisted of seals (75.9 ± 4.7%) and/or fish (20.4 ± 2.4%), mainly mackerel, which was consistent with stomach content data and limited literature on this population. Given the remote habitats and below surface feeding of most cetaceans, this newly developed cetacean-specific QFASA method, which can be applied to outer-layer biopsies, offers promise to provide a significant new understanding of diet dynamics of free-ranging odontocetes and perhaps other cetacean species throughout the world's oceans., (© 2022. The Author(s).)

Gut microbiomes were analyzed by 16S rRNA gene metabarcoding for polar bears (Ursus maritimus) from the southern Beaufort Sea (SB), where sea ice loss has led to increased use of land-based food resources by bears, and from East Greenland (EG), where persistent sea ice has allowed hunting of ice-associated prey nearly year-round. SB polar bears showed a higher number of total (940 vs. 742) and unique (387 vs. 189) amplicon sequence variants and higher inter-individual variation compared to EG polar bears. Gut microbiome composition differed significantly between the two subpopulations and among sex/age classes, likely driven by diet variation and ontogenetic shifts in the gut microbiome. Dietary tracer analysis using fatty acid signatures for SB polar bears showed that diet explained more intrapopulation variation in gut microbiome composition and diversity than other tested variables, i.e., sex/age class, body condition, and capture year. Substantial differences in the SB gut microbiome relative to EG polar bears, and associations between SB gut microbiome and diet, suggest that the shifting foraging habits of SB polar bears tied to sea ice loss may be altering their gut microbiome, with potential consequences for nutrition and physiology., (© 2022. The Author(s).)

The gut microbiota may modulate the disposition and toxicity of environmental contaminants within a host but, conversely, contaminants may also impact gut bacteria. Such contaminant-gut microbial connections, which could lead to alteration of host health, remain poorly known and are rarely studied in free-ranging wildlife. The polar bear (Ursus maritimus) is a long-lived, wide-ranging apex predator that feeds on a variety of high trophic position seal and cetacean species and, as such, is exposed to among the highest levels of biomagnifying contaminants of all Arctic species. Here, we investigate associations between mercury (THg; a key Arctic contaminant), diet, and the diversity and composition of the gut microbiota of polar bears inhabiting the southern Beaufort Sea, while accounting for host sex, age class and body condition. Bacterial diversity was negatively associated with seal consumption and mercury, a pattern seen for both Shannon and Inverse Simpson alpha diversity indices (adjusted R 2  = 0.35, F 1,18  = 8.00, P = 0.013 and adjusted R 2  = 0.26, F 1,18  = 6.04, P = 0.027, respectively). No association was found with sex, age class or body condition of polar bears. Bacteria known to either be involved in THg methylation or considered to be highly contaminant resistant, including Lactobacillales, Bacillales and Aeromonadales, were significantly more abundant in individuals that had higher THg concentrations. Conversely, individuals with higher THg concentrations showed a significantly lower abundance of Bacteroidales, a bacterial order that typically plays an important role in supporting host immune function by stimulating intraepithelial lymphocytes within the epithelial barrier. These associations between diet-acquired mercury and microbiota illustrate a potentially overlooked outcome of mercury accumulation in polar bears., (© 2021. The Author(s).)

We investigated short-chain (C 10-13 ) chlorinated paraffins (SCCP) in an Arctic marine food web. In zooplankton, fishes, and ringed seals from western Hudson Bay, Canada, SCCP concentrations ranged from 38.3 to 687 ng g -1 lipid weight. Monte Carlo-simulated trophic-adjusted biomagnification factors of individual SCCP congeners ranged from 0.07 to 0.55 for small pelagic fishes to seals. Despite relatively high concentrations in fishes, biomagnification of SCCPs within this food web appears limited. Environ Toxicol Chem 2021;40:2990-2999. © 2021 SETAC., (© 2021 SETAC.)

Interindividual variation in prey specialization is an essential yet overlooked aspect of wildlife feeding ecology, especially as it relates to intrapopulation variation in exposure to toxic contaminants. Here, we assessed blubber concentrations of an extensive suite of persistent organic pollutants in Icelandic killer whales ( Orcinus orca ). Polychlorinated biphenyl (PCB) concentrations in blubber were >300-fold higher in the most contaminated individual relative to the least contaminated, ranging from 1.3 to 428.6 mg·kg -1 lw. Mean PCB concentrations were 6-to-9-fold greater in individuals with a mixed diet including marine mammals than in fish specialist individuals, whereas males showed PCB concentrations 4-fold higher than females. Given PCBs have been identified as potentially impacting killer whale population growth, and levels in mixed feeders specifically exceeded known thresholds, the ecology of individuals must be recognized to accurately forecast how contaminants may threaten the long-term persistence of the world's ultimate marine predator.

Rising global demand for energy promotes extensive mining of natural resources, such as oil sands extractions in Alberta, Canada. These extractive activities release hazardous chemicals into the environment, such as polycyclic aromatic compounds (PACs), which include the parent polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and sulfur-containing heterocyclic dibenzothiophenes (DBTs). In areas adjacent to industrial installations, Indigenous communities may be exposed to these PACs through the consumption of traditional foods. Our objective was to evaluate and compare the concentrations of total PACs (∑PAC), expressed as the sum of the 16 U.S. EPA priority PAHs (∑PAH), 49 alkylated PAHs (∑alkyl-PAH), and 7 DBTs (∑DBT) in plant and animal foods collected in 2015 by the Bigstone Cree Nation in Alberta, Canada. We analyzed 42 plant tissues, 40 animal muscles, 5 ribs, and 4 pooled liver samples. Concentrations of ∑PAC were higher in the lichen, old man's beard (Usnea spp.) (808 ± 116 ng g -1 w.w.), than in vascular plants, and were also higher in smoked moose (Alces alces) rib (461 ± 120 ng g -1 w.w.) than in all other non-smoked animal samples. Alkylated-PAHs accounted for between 63% and 95% of ∑PAC, while the concentrations of ∑PAH represented 4%-36% of ∑PAC. Contributions of ∑DBT to ∑PAC were generally lowest, ranging from <1% to 14%. While the concentrations of benzo(a)pyrene (B[a]P) and ∑PAH4 (∑benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and B[a]P) in all samples were below guideline levels for human consumption as determined by the European Commission, guideline levels for the more prevalent alkylated PAHs are not available. Given the predominance of alkylated PAHs in all food samples and the potentially elevated toxicity relative to parent PAHs of this class of PACs, it is critical to consider a broader range of PACs other than just parent PAHs in research conducted close to oil sands mining activities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Assessing polar bear (Ursus maritimus) immune function in relation to environmental stressors, including habitat change, nutritional stress, pathogen prevalence, and pollution, has been identified as critical for improved understanding of the species' health. The objectives of this study were two-fold: 1) to assess the role of climate-associated factors (habitat use, body condition) in explaining the plasma concentrations of contaminants in southern Beaufort Sea (SB) polar bears, and 2) to investigate how climate-associated factors, contaminant concentrations, and pathogen sero-prevalence influence the plasma concentrations of immune-signaling proteins called cytokines. A commercially available multiplex canine cytokine panel was validated for the quantification of five pro- and anti-inflammatory cytokines in polar bear plasma: tumor necrosis factor alpha (TNF-α), interleukin 6 (IL-6), IL-8, IL-10, and interferon gamma-induced protein 10 (IP-10). This panel was then used to measure cytokine concentrations in 49 SB polar bears sampled in the springs of 2013 and 2014. Mean ∑PCBs (plasma), ∑OCs (plasma), and THg (hair) were 13.01 ± 1.52 ng g -1 w.w. (range: 0.17-52.63), 19.46 ± 1.17 ng g -1 w.w. (range: 6.63-45.82), and 0.49 μg g -1 d.w. (range: 0.99-15.18), respectively. Top models explaining variation in concentrations of plasma PCBs, plasma OC pesticides, and hair THg in SB polar bears included body mass index and/or habitat use (onshore versus offshore), with higher contaminant concentrations in leaner and/or offshore bears. Plasma cytokine concentrations were influenced most strongly by plasma PCBs and age, with little to no influence found for plasma OCs or hair THg concentrations, habitat use, or pathogen sero-prevalence. The lack of association between cytokines and these latter variables is likely due to a temporal disconnect between measured endpoints. The change of polar bear habitat use, feeding ecology, and body condition with ongoing climate warming is affecting exposure to contaminants and pathogens, with potential adverse consequences on a well-balanced immune system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Traditional foods provide nutritional, social, and economic benefits for Indigenous communities; however, anthropogenic activities have raised concerns about mercury (Hg), especially methylmercury (MeHg), in these foods. This issue may be of particular concern for communities near large industrial activities, including the Bigstone Cree Nation adjacent to the Athabasca oil sands region, Canada. This community-led study sought to assess variation in THg and MeHg concentrations among traditional food types (plants or animals), species, and tissues (muscles, organs), and variation in concentrations of the micronutrient selenium (Se)- thought to protect against Hg toxicity-and Se:THg ratios. Thirteen plant and animal species were collected in 2015 by Bigstone Cree community members. We quantified THg, Se, and Se:THg ratios in 65 plant and 111 animal samples and MeHg in 106 animal samples. For plants, the lichen, old man's beard (Usnea spp.), showed the highest concentrations of THg and Se (0.11 ± 0.02 and 0.08 ± 0.01 μg g -1 w. w., respectively) and also had a low Se:THg molar ratio. Concentrations of THg, MeHg, and Se differed among animal samples (P < 0.010), showing variation among species and among tissues/organs. Generally, concentrations of THg and MeHg were highest in aquatic animals, which also had relatively low Se:THg molar ratios. Overall results revealed substantial variation in the patterns of THg, MeHg, Se and Se:THg ratios across this comprehensive basket of traditional foods. Thus, measuring concentrations of THg alone, without considering MeHg and potential associations with Se, may not adequately convey the exposure to Hg in traditional foods., Competing Interests: Declaration of competing interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Polar bears ( Ursus maritimus ) from the southern Beaufort Sea (SB) subpopulation have traditionally fed predominantly upon ice-seals; however, as the proportion of the subpopulation using onshore habitat has recently increased, foraging on land-based resources, including remains of subsistence-harvested bowhead whales ( Balaena mysticetus ) and colonial nesting seabirds has been observed. Adipose tissue samples were collected from this subpopulation during the springs of 2013-2016 and analyzed for fatty acid signatures. Diet estimates were generated for the proportional consumption of ringed seal ( Pusa hispida ), bearded seal ( Erignathus barbatus ), and beluga whale ( Delphinapterus leucas ), relative to onshore foods, including bowhead whale remains and seabird, as represented by black guillemot ( Cepphus grylle mandtii ) nestlings and eggs. Quantitative fatty acid signature analysis (QFASA) estimated that the ice-obligate prey, ringed seal, remained the predominant prey species of SB polar bears (46.4 ± 1.8%), with much lower consumption of bearded seal (19.6 ± 2.0%), seabird (17.0 ± 1.2%), bowhead whale (15.0 ± 1.4%), and hardly any beluga whale (2.0 ± 0.5%). Adult and subadult females appeared to depend more on the traditional ringed seal prey than adult and subadult males. Diet estimates of SB polar bears showed significant interannual variability for all prey ( F 12, 456  = 3.17, p  < .001). Longer-term estimates suggested that both types of onshore prey, bowhead whale remains and seabird, have represented a moderate proportion of the food resources used by SB polar bears since at least the start of the 21st Century., Competing Interests: None declared., (© 2020 The Authors. Ecology and Evolution published by John Wiley & Sons Ltd.)

The gut microbiota plays a critical role in host health, yet remains poorly studied in wild species. Polar bears (Ursus maritimus), key indicators of Arctic ecosystem health and environmental change, are currently affected by rapid shifts in habitat that may alter gut homeostasis. Declining sea ice has led to a divide in the southern Beaufort Sea polar bear subpopulation such that an increasing proportion of individuals now inhabit onshore coastal regions during the open-water period ('onshore bears') while others continue to exhibit their typical behaviour of remaining on the ice ('offshore bears'). We propose that bears that have altered their habitat selection in response to climate change will exhibit a distinct gut microbiota diversity and composition, which may ultimately have important consequences for their health. Here, we perform the first assessment of abundance and diversity in the faecal microbiota of wild polar bears using 16S rRNA Illumina technology. We find that bacterial diversity is significantly higher in onshore bears compared to offshore bears. The most enriched OTU abundance in onshore bears belonged to the phylum Proteobacteria, while the most depleted OTU abundance within onshore bears was seen in the phylum Firmicutes. We conclude that climate-driven changes in polar bear land use are associated with distinct microbial communities. In doing so, we present the first case of global change mediated alterations in the gut microbiota of a free-roaming wild animal.

We quantified blubber concentrations of vitamins A (retinol) and E (α-tocopherol) and evaluated associations with persistent organic pollutants (ΣPOPs) in 14 highly-contaminated killer whales (Orcinus orca) sampled in Greenland from 2012 to 2014. We considered the influence of blubber depth, sex/age class and diet (based on biomass % of major fatty acids) in these relationships. Blubber concentrations of vitamin A averaged 34.1 ± 4.7 μg g -1 wet weight (ww) and vitamin E averaged 35.6 ± 4.4 μg g -1 ww. Although overall vitamin A concentrations did not vary between inner (closer to the muscle) and outer (closer to the skin) blubber layer or between sub-adults and adult females, concentrations in the outer layer of sub-adults were lower compared to the outer layer of adult females (p = 0.03). Outer layer may therefore reflect age accumulation of vitamin A, while in the more active inner layer, age effects might be masked by metabolic needs such as lactation. Neither diet nor ΣPOPs affected vitamin A variation, suggesting this vitamin is highly regulated in the body. Given the high exposures in these killer whales, vitamin A might not be a sensitive biomarker for POPs adverse effects. Vitamin E concentrations were significantly higher in inner compared to outer layer (p < 0.001), likely associated with blubber composition, suggesting that biopsies may not fully represent vitamin E concentrations in blubber. Age-accumulation of vitamin E also occurred with higher concentrations in adult females compared to sub-adults, independent of blubber depth (p < 0.01). Diet, ΣPOPs, and an interaction between these two variables significantly affected vitamin E variation in inner blubber, explaining 91% of this variation. The negative relationship between ΣPOPs (especially Σdichlorodiphenyltrichloroethane (DDT) and Σchlordanes in outer layers) and vitamin E was observed only in killer whales with a diet poorer in polyunsaturated fatty acids, suggested that killer whales feeding more consistently on marine mammals in Arctic environments over a fish-based diet, may be at higher risk of POP-induced disruption in vitamin E homeostasis. Considering diet is therefore important to understand the potential effects of elevated contaminant exposures on levels of certain essential nutrients, i.e., vitamin E, in killer whales., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The polar bear (Ursus maritimus) is among the Arctic species exposed to the highest concentrations of long-range transported bioaccumulative contaminants, such as halogenated organic compounds and mercury. Contaminant exposure is considered to be one of the largest threats to polar bears after the loss of their Arctic sea ice habitat due to climate change. The aim of this review is to provide a comprehensive summary of current exposure, fate, and potential health effects of contaminants in polar bears from the circumpolar Arctic required by the Circumpolar Action Plan for polar bear conservation. Overall results suggest that legacy persistent organic pollutants (POPs) including polychlorinated biphenyls, chlordanes and perfluorooctane sulfonic acid (PFOS), followed by other perfluoroalkyl compounds (e.g. carboxylic acids, PFCAs) and brominated flame retardants, are still the main compounds in polar bears. Concentrations of several legacy POPs that have been banned for decades in most parts of the world have generally declined in polar bears. Current spatial trends of contaminants vary widely between compounds and recent studies suggest increased concentrations of both POPs and PFCAs in certain subpopulations. Correlative field studies, supported by in vitro studies, suggest that contaminant exposure disrupts circulating levels of thyroid hormones and lipid metabolism, and alters neurochemistry in polar bears. Additionally, field and in vitro studies and risk assessments indicate the potential for adverse impacts to polar bear immune functions from exposure to certain contaminants., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We determined concentrations of eicosapentaenoic and docosahexaenoic acids (EPA + DHA), Σomega-3, polyunsaturated fatty acids (ΣPUFA), selenium, methylmercury, and selenium:methylmercury (Se:Hg) ratios in native and northward-redistributing sub-Arctic marine fish and invertebrates from low, mid-, and high Canadian Arctic latitudes. There was no clear latitudinal trend in nutrient or contaminant concentrations. Among species, EPA + DHA concentrations in native Arctic cod (Boreogadus saida) were similar to concentrations in sub-Arctic capelin (Mallotus villosus) and sand lance (Ammodytes spp.) (444-658 mg.100 g -1 ), and higher than in most other species. Concentrations of EPA + DHA were related to lipid content, but to a greater extent for higher trophic position species (R 2  = 0.83) than for species at lower trophic positions (R 2  = 0.61). Selenium concentrations were higher in sand lance (1.15 ± 0.16 μg g -1 ) than in all other species (0.30-0.69 μg g -1 ), which was significantly, but weakly, explained by more pelagic feeding in sand lance. Methylmercury concentrations were similar (and Se:Hg ratios were higher) in capelin, sand lance, and Arctic cod (0.01-0.03 μg g -1 wet weight (ww)) and lower than in other prey (0.12-0.26 μg g -1 ww), which was significantly explained by the smaller size of these species and more pelagic feeding habits than other fish. These results suggested that a shift in prey fish composition from Arctic cod to capelin and/or sand lance is unlikely to reduce the food quality of the prey available to marine predators at least with respect to concentrations of essential fatty acids, selenium, and Se:Hg ratios., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Sightings of killer whales (Orcinus orca) in Greenland have increased in recent years, coincident with sea ice loss. These killer whales are likely from fish-feeding North Atlantic populations, but may have access to marine mammal prey in Greenlandic waters, which could lead to increased exposures to biomagnifying contaminants. Most studies on polychlorinated biphenyl (PCB) and organochlorine (OC) contaminants in killer whales have used biopsies which may not be representative of contaminant concentrations through the entire blubber depth. Here, we measured PCB and OC concentrations in 10 equal-length blubber sections of 18 killer whales harvested in southeast Greenland (2012-2014), and 3 stranded in the Faroe Islands (2008) and Denmark (2005). Overall, very high concentrations of ΣPCB, Σchlordanes (ΣCHL), and Σdichlorodiphenyltrichloroethane (ΣDDT) were found in the southeast Greenland and Denmark individuals (means of ~40 to 70mgkg -1 lipid weight). These concentrations were higher than in the Faroe Island individuals (means of ~2 to 5mgkg -1 lipid weight) and above those previously reported for other fish-feeding killer whales in the North Atlantic, likely in part due to additional feeding on marine mammals. On a wet weight basis, concentrations of all contaminants were significantly lower in the outermost blubber layer (0.15-0.65cm) compared to all other layers (p<0.01), except for Σhexachlorocyclohexanes. However, after lipid correction, no variation was found for ΣCHL and Σchlorobenzene concentrations, while the outermost layer(s) still showed significantly lower ΣPCB, ΣDDT, Σmirex, Σendosulfan, and dieldrin concentrations than one or more of the inner layers. Yet, the magnitude of these differences was low (up to 2-fold) suggesting that a typical biopsy may be a reasonable representation of the PCB and OC concentrations reported in killer whales, at least on a lipid weight basis., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Recent decline of sea ice habitat has coincided with increased use of land by polar bears (Ursus maritimus) from the southern Beaufort Sea (SB), which may alter the risks of exposure to pathogens and contaminants. We assayed blood samples from SB polar bears to assess prior exposure to the pathogens Brucella spp., Toxoplasma gondii, Coxiella burnetii, Francisella tularensis, and Neospora caninum, estimate concentrations of persistent organic pollutants (POPs), and evaluate risk factors associated with exposure to pathogens and POPs. We found that seroprevalence of Brucella spp. and T. gondii antibodies likely increased through time, and provide the first evidence of exposure of polar bears to C. burnetii, N. caninum, and F. tularensis. Additionally, the odds of exposure to T. gondii were greater for bears that used land than for bears that remained on the sea ice during summer and fall, while mean concentrations of the POP chlordane (ΣCHL) were lower for land-based bears. Changes in polar bear behavior brought about by climate-induced modifications to the Arctic marine ecosystem may increase exposure risk to certain pathogens and alter contaminant exposure pathways.

Contaminant dynamics within Arctic marine food webs may be altered through the climate-driven northward invasions of temperate/boreal species. Here, we compare tissue concentrations of total mercury (THg) and legacy and emerging persistent organic pollutants (POPs) in native versus invading forage species sampled from 2012 to 2014 near Arviat, Clyde River, and Resolute Bay, NU, representing, low, mid- and high eastern Canadian Arctic regions, respectively. Concentrations of THg, legacy Σ-polychlorinated biphenyls (ΣPCB) and Σ-organochlorine (ΣOC) pesticides were detected in all forage species, whereas emerging halogenated flame retardants were detected in only a few individuals. Concentrations of major contaminant groups among regions did not vary for Arctic cod (Boreogadus saida), while for sculpin (Cottoidea) there was no clear latitudinal trend. Thus, considering interspecific variation, native sculpin and northern shrimp (Pandalus borealis) had the highest overall concentrations of THg (0.17 ± 0.02 and 0.21 ± 0.01 μg g -1 wet weight, respectively), ΣPCB (322 ± 35 and 245 ± 25 ng g -1 lipid weight (lw), respectively), and ΣOC (413 ± 38 and 734 ± 64 ng g -1 lw, respectively). Comparing the keystone native species, Arctic cod, to its 'replacement' species, capelin (Mallotus villosus) and sandlance (Ammodytes spp.), THg concentrations were higher in Arctic cod compared to capelin (p < 0.001), which was partly explained by differences in fish length. Conversely, capelin and sandlance had higher concentrations of most POPs than Arctic cod (p < 0.02). Neither feeding habitat (based on δ 13 C), trophic position (based on δ 15 N), nor fish length significantly explained these differences in POPs between Arctic cod, capelin and sandlance. Higher POPs concentrations, as well as variation in congener/compound patterns, in capelin and sandlance relative to Arctic cod seem, therefore, more likely related to a more "temperate"-type contaminant signature in the invaders. Nevertheless, the relatively small (up to two-fold) magnitude of these differences suggested limited effects of these ecological changes on contaminant uptake by Arctic piscivores., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We evaluated total mercury (THg) concentrations and trends in polar bears from the southern Beaufort Sea subpopulation from 2004 to 2011. Hair THg concentrations ranged widely among individuals from 0.6 to 13.3 μg g -1 dry weight (mean: 3.5 ± 0.2 μg g -1 ). Concentrations differed among sex and age classes: solitary adult females ≈ adult females with cubs ≈ subadults > adult males ≈ yearlings > cubs-of-the-year ≈ 2 year old dependent cubs. No variation was observed between spring and fall samples. For spring-sampled adults, THg concentrations declined by 13% per year, contrasting recent trends observed for other Western Hemispheric Arctic biota. Concentrations also declined by 15% per year considering adult males only, while a slower, nonsignificant decrease of 4.4% per year was found for adult females. Lower THg concentrations were associated with higher body mass index (BMI) and higher proportions of lower trophic position food resources consumed. Because BMI and diet were related, and the relationship to THg was strongest for BMI, trends were re-evaluated adjusting for BMI as the covariate. The adjusted annual decline was not significant. These findings indicate that changes in foraging ecology, not declining environmental concentrations of mercury, are driving short-term declines in THg concentrations in southern Beaufort Sea polar bears.

The distribution of current-use pesticides (CUPs) in seawater and their trophodynamics were investigated in 3 Canadian Arctic marine food chains. The greatest ranges of dissolved-phase concentrations in seawater for each CUP were endosulfan sulfate (less than method detection limit (MDL) to 19 pg L(-1) ) > dacthal (0.76-15 pg L(-1) ) > chlorpyrifos (less than MDL to 8.1 pg L(-1) ) > pentachloronitrobenzene (less than MDL to 2.6 pg L(-1) ) > α-endosulfan (0.20-2.3 pg L(-1) ). Bioaccumulation factors (BAFs, water-respiring organisms) were greatest in plankton, including chlorothalonil (log BAF = 7.4 ± 7.1 L kg(-1) , mean ± standard error), chlorpyrifos (log BAF = 6.9 ± 6.7 L kg(-1) ), and α-endosulfan (log BAF = 6.5 ± 6.0 L kg(-1) ). The largest biomagnification factors (BMFs) were found for dacthal in the capelin:plankton trophic relationship (BMF = 13 ± 5.0) at Cumberland Sound (Nunvavut), and for β-endosulfan (BMF = 16 ± 4.9) and α-endosulfan (BMF = 9.3 ± 2.8) in the polar bear-ringed seal relationship at Barrow and Rae Strait (NU), respectively. Concentrations of endosulfan sulfate exhibited trophic magnification (increasing concentrations with increasing trophic level) in the poikilothermic portion of the food web (trophic magnification factor = 1.4), but all of the CUPs underwent trophic dilution in the marine mammal food web, despite some trophic level-specific biomagnification. Together, these observations are most likely indicative of metabolism of these CUPs in mammals. Environ Toxicol Chem 2016;35:1695-1707. © 2016 SETAC., (© 2016 SETAC.)

In the Arctic Ocean's southern Beaufort Sea (SB), the length of the sea ice melt season (i.e., period between the onset of sea ice break-up in summer and freeze-up in fall) has increased substantially since the late 1990s. Historically, polar bears (Ursus maritimus) of the SB have mostly remained on the sea ice year-round (except for those that came ashore to den), but recent changes in the extent and phenology of sea ice habitat have coincided with evidence that use of terrestrial habitat is increasing. We characterized the spatial behavior of polar bears spending summer and fall on land along Alaska's north coast to better understand the nexus between rapid environmental change and increased use of terrestrial habitat. We found that the percentage of radiocollared adult females from the SB subpopulation coming ashore has tripled over 15 years. Moreover, we detected trends of earlier arrival on shore, increased length of stay, and later departure back to sea ice, all of which were related to declines in the availability of sea ice habitat over the continental shelf and changes to sea ice phenology. Since the late 1990s, the mean duration of the open-water season in the SB increased by 36 days, and the mean length of stay on shore increased by 31 days. While on shore, the distribution of polar bears was influenced by the availability of scavenge subsidies in the form of subsistence-harvested bowhead whale (Balaena mysticetus) remains aggregated at sites along the coast. The declining spatio-temporal availability of sea ice habitat and increased availability of human-provisioned resources are likely to result in increased use of land. Increased residency on land is cause for concern given that, while there, bears may be exposed to a greater array of risk factors including those associated with increased human activities.

Conservation concern regarding the overharvest of global shark populations for meat and fin consumption largely surrounds documented deleterious ecosystem effects, but may be further supported by improved knowledge of possibly high levels in their edible tissues (particularly meat) of the neurotoxin, methylmercury (CH3Hg). For many regions, however, little data exist on shark tissue Hg concentrations, and reasons for Hg variation within and among species or across regions are poorly understood. We quantified total Hg (THg) in 17 shark species (total n=283) from the east coast of South Africa, a top Hg emitter globally. Concentrations varied from means of around 0.1 mg kg(-1) dry weight (dw) THg in hardnose smoothhound (Mustelus mosis) and whale (Rhincodon typus) sharks to means of over 10 mg kg(-1) dw in shortfin mako (Isurus oxyrinchus), scalloped hammerhead (Sphyrna lewini), white (Carcharodon carcharias) and ragged-tooth (Carcharias taurus) sharks. These sharks had higher THg levels than conspecifics sampled from coastal waters of the North Atlantic and North, mid-, and South Pacific, and although sampling year and shark size may play a confounding role, this result suggests the potential importance of elevated local emissions. Values of THg showed strong, species-specific correlations with length, and nearly half the remaining variation was explained by trophic position (using nitrogen stable isotopes, δ(15)N), whereas measures of foraging habitat (using carbon stable isotopes, δ(13)C) were not significant. Mercury concentrations were above the regulatory guidelines for fish health effects and safe human consumption for 88% and 70% of species, respectively, suggesting on-going cause for concern for shark health, and human consumers of shark meat., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Polar bears (Ursus maritimus) consume large quantities of seal blubber and other high trophic marine mammals and consequently have some of the highest tissue concentrations of organohalogen contaminants (OHCs) among Arctic biota. In the present paper we carried out a risk quotient (RQ) evaluation on OHC-exposed polar bears harvested from 1999 to 2008 and from 11 circumpolar subpopulations spanning from Alaska to Svalbard in order to evaluate the risk of OHC-mediated reproductive effects (embryotoxicity, teratogenicity), immunotoxicity and carcinogenicity (genotoxicity). This RQ evaluation was based on the Critical Body Residue (CBR) concept and a Physiologically-Based Pharmacokinetic Modelling (PBPK) approach using OHC concentrations measured in polar bear adipose or liver tissue. The range of OHC concentrations within polar bear populations were as follows for adipose, sum polychlorinated biphenyls ∑PCBs (1797-10,537 ng/g lw), sum methylsulphone-PCB ∑MeSO2-PCBs (110-672 ng/g lw), sum chlordanes ∑CHLs (765-3477 ng/g lw), α-hexachlorocyclohexane α-HCH (8.5-91.3 ng/g lw), β-hexachlorocyclohexane β-HCH (65.5-542 ng/g lw), sum chlorbenzenes ∑ClBzs (145-304 ng/g lw), dichlorodiphenyltrichloroethane ∑DDTs (31.5-206 ng/g lw), dieldrin (69-249 ng/g lw), polybrominated diphenyl ethers ∑PBDEs (4.6-78.4 ng/g lw). For liver, the perfluorooctanesulfonic acid (PFOS) concentrations ranged from 231-2792 ng/g ww. The total additive RQ from all OHCs ranged from 4.3 in Alaska to 28.6 in East Greenland bears for effects on reproduction, immune health and carcinogenicity, highlighting the important result that the toxic effect threshold (i.e. RQ>1) was exceeded for all polar bear populations assessed. PCBs were the main contributors for all three effect categories, contributing from 70.6% to 94.3% of the total risk and a RQ between 3.8-22.5. ∑MeSO2-PCBs were the second highest effect contributor for reproductive and immunological effects (0.17

Perfluorooctane sulfonate (PFOS) has been reported to be among the most concentrated persistent organic pollutants in Arctic marine wildlife. The present study examined the in vitro depletion of major PFOS precursors, N-ethyl-perfluorooctane sulfonamide (N-EtFOSA) and perfluorooctane sulfonamide (FOSA), as well as metabolite formation using an assay based on enzymatically viable liver microsomes for three top Arctic marine mammalian predators, polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas), and ringed seal (Pusa hispida), and in laboratory rat (Rattus rattus) serving as a general mammalian model and positive control. Rat assays showed that N-EtFOSA (38 nM or 150 ng mL(-1)) to FOSA metabolism was >90% complete after 10 min, and at a rate of 23 pmol min(-1) mg(-1) protein. Examining all species in a full 90 min incubation assay, there was >95% N-EtFOSA depletion for the rat active control and polar bear microsomes, ∼65% for ringed seals, and negligible depletion of N-EtFOSA for beluga whale. Concomitantly, the corresponding in vitro formation of FOSA from N-EtFOSA was also quantitatively rat≈polar bear>ringed seal>>>beluga whale. A lack of enzymatic ability and/or a rate too slow to be detected likely explains the lack of N-EtFOSA to FOSA transformation for beluga whale. In the same assays, the depletion of the FOSA metabolite was insignificant (p>0.01) and with no concomitant formation of PFOS metabolite. This suggests that, in part, a source of FOSA is the biotransformation of accumulated N-EtFOSA in free-ranging Arctic ringed seal and polar bear., (Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.)

Polychlorinated biphenyls (PCBs) chiral signatures were measured in Greenland sharks (Somniosus microcephalus) and their potential prey in arctic marine food webs from Canada (Cumberland Sound) and Europe (Svalbard) to assess temporal and spatial variation in PCB contamination at the stereoisomer level. Marine mammals had species-specific enantiomer fractions (EFs), likely due to a combination of in vivo biotransformation and direct trophic transfer. Greenland sharks from Cumberland Sound in 2007-2008 had similar EFs to those sharks collected a decade ago in the same location (PCBs 91, 136 and 149) and also similar to their conspecifics from Svalbard for some PCB congeners (PCBs 95, 136 and 149). However, other PCB EFs in the sharks varied temporally (PCB 91) or spatially (PCB 95), suggesting a possible spatiotemporal variation in their diets, since biotransformation capacity was unlikely to have varied within this species from region to region or over the time frame studied., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Body condition is a key indicator of individual and population health. Yet, there is little consensus as to the most appropriate condition index (CI), and most of the currently used CIs have not been thoroughly validated and are logistically challenging. Adipose samples from large datasets of capture biopsied, remote biopsied, and harvested polar bears were used to validate adipose lipid content as a CI via tests of accuracy, precision, sensitivity, biopsy depth, and storage conditions and comparisons to established CIs, to measures of health and to demographic and ecological parameters. The lipid content analyses of even very small biopsy samples were highly accurate and precise, but results were influenced by tissue depth at which the sample was taken. Lipid content of capture biopsies and samples from harvested adult females was correlated with established CIs and/or conformed to expected biological variation and ecological changes. However, lipid content of remote biopsies was lower than capture biopsies and harvested samples, possibly due to lipid loss during dart retrieval. Lipid content CI is a biologically relevant, relatively inexpensive and rapidly assessed CI and can be determined routinely for individuals and populations in order to infer large-scale spatial and long-term temporal trends. As it is possible to collect samples during routine harvesting or remotely using biopsy darts, monitoring and assessment of body condition can be accomplished without capture and handling procedures or noninvasively, which are methods that are preferred by local communities. However, further work is needed to apply the method to remote biopsies.

Legacy organochlorine contaminants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28years between 1983 and 2010. Of 19 major legacy contaminants and congeners (ΣPCB, 4 PCB congeners (CB153, 180, 170/190), ΣDDT, p,p'-DDE, p,p' -DDD and p,p'-DDT, α- and β-hexachlorocyclohexane (HCH), HCB, octachlorostyrene, dieldrin, oxychlordane, cis- and trans-chlordane, cis- and trans-nonachlor, heptachlor epoxide and BB-153), 18 showed statistically significant average yearly declines of -4.4% (range: -2.0 to -10.8%/year) among subadult polar bears (i.e. females<5years, males<6years). For example, the ∑PCB concentrations declined 2.7 fold from 22730ng/g lw (95% C.I.: 12470-32990ng/g lw) in 1983-1986 to 8473ng/g lw (95% C.I.: 6369-9776ng/g lw) in 2006-2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Despite declines as a result of international regulations, relatively high levels of these historic pollutants persist in East Greenland polar bear tissues., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Brominated flame retardants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28years between 1983 and 2010. Significant linear increases were found for sum polybrominated diphenyl ether (ΣPBDE), BDE100, BDE153, and hexabromocyclododecane (HBCD). Average increases of 5.0% per year (range: 2.9-7.6%/year) were found for the subadult polar bears. BDE47 and BDE99 concentrations did not show a significant linear trend over time, but rather a significant non-linear trend peaking between 2000 and 2004. The average ΣPBDE concentrations increased 2.3 fold from 25.0ng/g lw (95% C.I.: 15.3-34.7ng/g lw) in 1983-1986 to 58.5ng/g lw (95% C.I.: 43.6-73.4ng/g lw) in 2006-2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Analyses of δ(15)N and δ(13)C stable isotopes in hair revealed no clear linear temporal trends in trophic level or carbon source, respectively, and non-linear trends differed among sex and age groups. These increasing concentrations of organobromine contaminants contribute to complex organohalogen mixture, already causing health effects to the East Greenland polar bears., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Rapid climate changes are occurring in the Arctic, with substantial repercussions for arctic ecosystems. It is challenging to assess ecosystem changes in remote polar environments, but one successful approach has entailed monitoring the diets of upper trophic level consumers. Quantitative fatty acid signature analysis (QFASA) and fatty acid carbon isotope (δ(13) C-FA) patterns were used to assess diets of East Greenland (EG) polar bears (Ursus maritimus) (n = 310) over the past three decades. QFASA-generated diet estimates indicated that, on average, EG bears mainly consumed arctic ringed seals (47.5 ± 2.1%), migratory subarctic harp (30.6 ± 1.5%) and hooded (16.7 ± 1.3%) seals and rarely, if ever, consumed bearded seals, narwhals or walruses. Ringed seal consumption declined by 14%/decade over 28 years (90.1 ± 2.5% in 1984 to 33.9 ± 11.1% in 2011). Hooded seal consumption increased by 9.5%/decade (0.0 ± 0.0% in 1984 to 25.9 ± 9.1% in 2011). This increase may include harp seal, since hooded and harp seal FA signatures were not as well differentiated relative to other prey species. Declining δ(13) C-FA ratios supported shifts from more nearshore/benthic/ice-associated prey to more offshore/pelagic/open-water-associated prey, consistent with diet estimates. Increased hooded seal and decreased ringed seal consumption occurred during years when the North Atlantic Oscillation (NAO) was lower. Thus, periods with warmer temperatures and less sea ice were associated with more subarctic and less arctic seal species consumption. These changes in the relative abundance, accessibility, or distribution of arctic and subarctic marine mammals may have health consequences for EG polar bears. For example, the diet change resulted in consistently slower temporal declines in adipose levels of legacy persistent organic pollutants, as the subarctic seals have higher contaminant burdens than arctic seals. Overall, considerable changes are occurring in the EG marine ecosystem, with consequences for contaminant dynamics., (© 2013 John Wiley & Sons Ltd.)

In the present study, the authors investigated the influence of carbon and lipid sources on regional differences in liver trace element (As, Cd, Cu, total Hg, Mn, Pb, Rb, Se, and Zn) concentrations measured in polar bears (Ursus maritimus) (n = 121) from 10 Alaskan, Canadian Arctic, and East Greenland subpopulations. Carbon and lipid sources were assessed using δ(13) C in muscle tissue and fatty acid (FA) profiles in subcutaneous adipose tissue as chemical tracers. A negative relationship between total Hg and δ(13) C suggested that polar bears feeding in areas with higher riverine inputs of terrestrial carbon accumulate more Hg than bears feeding in areas with lower freshwater input. Mercury concentrations were also positively related to the FA 20:1n-9, which is biosynthesized in large amounts in Calanus copepods. This result raises the hypothesis that Calanus glacialis are an important link in the uptake of Hg in the marine food web and ultimately in polar bears. Unadjusted total Hg, Se, and As concentrations showed greater geographical variation among polar bear subpopulations compared with concentrations adjusted for carbon and lipid sources. The Hg concentrations adjusted for carbon and lipid sources in Bering-Chukchi Sea polar bear liver tissue remained the lowest among subpopulations. Based on these findings, the authors suggest that carbon and lipid sources for polar bears should be taken into account when one is assessing spatial and temporal trends of long-range transported trace elements., (Copyright © 2012 SETAC.)