Cross-cutting studies of per- and polyfluorinated alkyl substances (PFAS) in Arctic wildlife and humans.

This cross-cutting review focuses on the presence and impacts of per- and polyfluoroalkyl substances (PFAS) in the Arctic. Several PFAS undergo long-range transport via atmospheric (volatile polyfluorinated compounds) and oceanic pathways (perfluorinated alkyl acids, PFAAs), causing widespread contamination of the Arctic. Beyond targeting a few well-known PFAS, applying sum parameters, suspect and non-targeted screening are promising approaches to elucidate predominant sources, transport, and pathways of PFAS in the Arctic environment, wildlife, and humans, and establish their time-trends. Across species, concentrations were dominated by perfluorooctanesulfonic acid (PFOS), followed by perfluorononanoic acid (PFNA); highest concentrations were present in mammalian livers and bird eggs. Time trends were similar for East Greenland ringed seals (Pusa hispida) and polar bears (Ursus maritimus). In polar bears, PFOS concentrations increased from the 1980s to 2006, with a secondary peak in 2014-2021, while PFNA increased regularly in the Canadian and Greenlandic ringed seals and polar bear livers. Human time trends vary regionally (though lacking for the Russian Arctic), and to the extent local Arctic human populations rely on traditional wildlife diets, such as marine mammals. Arctic human cohort studies implied that several PFAAs are immunotoxic, carcinogenic or contribute to carcinogenicity, and affect the reproductive, endocrine and cardiometabolic systems. Physiological, endocrine, and reproductive effects linked to PFAS exposure were largely similar among humans, polar bears, and Arctic seabirds. For most polar bear subpopulations across the Arctic, modeled serum concentrations exceeded PFOS levels in human populations, several of which already exceeded the established immunotoxic thresholds for the most severe risk category. Data is typically limited to the western Arctic region and populations. Monitoring of legacy and novel PFAS across the entire Arctic region, combined with proactive community engagement and international restrictions on PFAS production remain critical to mitigate PFAS exposure and its health impacts in the Arctic.

Effects of preparation on nutrient and environmental contaminant levels in Arctic beluga whale (Delphinapterus leucas) traditional foods.

For Canadian Arctic indigenous populations, marine mammal (MM) traditional foods (TFs) represent sources of both important nutrients and hazardous environmental contaminants. Food preparation is known to impact the nutrient and environmental contaminant content of processed items, yet the impacts of preparation on indigenous Arctic MM TFs remain poorly characterized. In order to determine how the various processes involved in preparing beluga blubber TFs affect their levels of nutrients and environmental contaminants, we collected blubber samples from 2 male beluga whales, aged 24 and 37 years, captured during the 2014 summer hunting season in Tuktoyaktuk, Northwest Territories, and processed them according to local TF preparation methods. We measured the levels of select nutrients [selenium (Se), polyunsaturated fatty acids (PUFAs)] and contaminants [organochlorine pesticides, perfluoroalkyl and polyfluoroalkyl substances (PFASs), polybrominated diphenyl ethers, polychlorinated biphenyls, polycyclic aromatic hydrocarbons (PAHs), mercury (Hg)] in raw and prepared (boiled, roasted, aged) beluga blubber TFs. The impacts of beluga blubber TF preparation methods on nutrient and environmental contaminant levels were inconsistent, as the majority of processes either did not appear to influence concentrations or affected the two belugas differently. However, roasting and ageing beluga blubber consistently impacted certain compounds: roasting blubber increased concentrations of hydrophilic substances (Se and certain PFASs) through solvent depletion and deposited PAHs from cookfire smoke. The solid-liquid phase separation involved in ageing blubber depleted hydrophilic elements (Se, Hg) and some ionogenic PFASs from the lipid-rich liquid oil phase, while PUFA levels appeared to increase, and hydrophobic persistent organic pollutants were retained. Ageing blubber adjacent to in-use smokehouses also resulted in considerable PAH deposition to processed samples. Our findings demonstrated that contaminant concentration differences were greater between the two sets of whale samples, based on age differences, than they were within each set of whale samples, due to variable preparation methods. When considering means to minimize human contaminant exposure while maximizing nutrient intake, consumption of aged liquid from younger male whales would be preferred, based on possible PUFA enhancement and selective depletion of hydrophilic environmental contaminants in this food item.

Assessment of neurotoxic effects of mercury in beluga whales (Delphinapterus leucas), ringed seals (Pusa hispida), and polar bears (Ursus maritimus) from the Canadian Arctic.

Marine mammals are indicator species of the Arctic ecosystem and an integral component of the traditional Inuit diet. The potential neurotoxic effects of increased mercury (Hg) in beluga whales (Delphinapterus leucas), ringed seals (Pusa hispida), and polar bears (Ursus maritimus) are not clear. We assessed the risk of Hg-associated neurotoxicity to these species by comparing their brain Hg concentrations with threshold concentrations for toxic endpoints detected in laboratory animals and field observations: clinical symptoms (>6.75 mg/kg wet weight (ww)), neuropathological signs (>4 mg/kg ww), neurochemical changes (>0.4 mg/kg ww), and neurobehavioral changes (>0.1mg/kg ww). The total Hg (THg) concentrations in the cerebellum and frontal lobe of ringed seals and polar bears were <0.5mg/kg ww, whereas the average concentration in beluga whale brain was >3mg/kg ww. Our results suggest that brain THg levels in polar bears are below levels that induce neurobehavioral effects as reported in the literature, while THg concentrations in ringed seals are within the range that elicit neurobehavioral effects and individual ringed seals exceed the threshold for neurochemical changes. The relatively high THg concentration in beluga whales exceeds all of the neurotoxicity thresholds assessed. High brain selenium (Se):Hg molar ratios were observed in all three species, suggesting that Se could protect the animals from Hg-associated neurotoxicity. This assessment was limited by several factors that influence neurotoxic effects in animals, including: animal species; form of Hg in the brain; and interactions with modifiers of Hg-associated toxicity, such as Se. Comparing brain Hg concentrations in wildlife with concentrations of appropriate laboratory studies can be used as a tool for risk characterization of the neurotoxic effects of Hg in Arctic marine mammals.

Molecular and neurochemical biomarkers in Arctic beluga whales (Delphinapterus leucas) were correlated to brain mercury and selenium concentrations.

Mercury (Hg) concentrations have increased in western Arctic beluga whales (Delphinapterus leucas) since the industrial revolution. Methylmercruy (MeHg) is a known neurotoxicant, yet little is known about the risk of exposure for beluga whales. Selenium (Se) has been linked to demethylation of MeHg in cetaceans, but its role in attenuating Hg toxicity in beluga whales is poorly understood. The objective of this study is to explore relationships between Hg and Se concentrations and neurochemical biomarkers in different brain regions of beluga whales in order to assess potential neurotoxicological risk of Hg exposure in this population. Brain tissue was sampled from hunter-harvested beluga whales from the western Canadian Arctic in 2008 and 2010. Neurochemical and molecular biomarkers were measured with radioligand binding assays and quantitative PCR, respectively. Total Hg (HgT) concentration ranged from 2.6-113 mg kg(-1) dw in temporal cortex. Gamma-amminobutyric acid type A receptor (GABAA-R) binding in the cerebellum was negatively associated with HgT, MeHg and total Se (SeT) concentrations (p ≤ 0.05). The expression of mRNA for GABAA-R subunit α2 was negatively associated with HgT and MeHg (p ≤ 0.05). Furthermore, GABAA-R binding was positively correlated to mRNA expression for GABAA-R α2 subunit, and negatively correlated to the expression of mRNA for GABAA-R α4 subunit (p ≤ 0.05). The expression of N-methyl-d-aspartate receptor (NMDA-R) subunit 2b mRNA expression was negatively associated with iHglabile concentration in the cerebellum (p ≤ 0.05). Variation of molecular and/or biochemical components of the GABAergic and glutamatergic signaling pathways were associated with MeHg exposure in beluga whales. Our results show that MeHg exposure is associated with neurochemical variation in the cerebellum of beluga whales and Se may partially protect from MeHg-associated neurotoxicity.

Mercury distribution and speciation in different brain regions of beluga whales (Delphinapterus leucas).

The toxicokinetics of mercury (Hg) in key species of Arctic ecosystem are poorly understood. We sampled five brain regions (frontal lobe, temporal lobe, cerebellum, brain stem and spinal cord) from beluga whales (Delphinapterus leucas) harvested in 2006, 2008, and 2010 from the eastern Beaufort Sea, Canada, and measured total Hg (HgT) and total selenium (SeT) by inductively coupled plasma mass spectrometry (ICP-MS), mercury analyzer or cold vapor atomic absorption spectrometry, and the chemical forms using a high performance liquid chromatography ICP-MS. At least 14% of the beluga whales had HgT concentrations higher than the levels of observable adverse effect (6.0 mg kg(-1) wet weight (ww)) in primates. The concentrations of HgT differed between brain regions; median concentrations (mgkg(-1) ww) were 2.34 (0.06 to 22.6, 81) (range, n) in temporal lobe, 1.84 (0.12 to 21.9, 77) in frontal lobe, 1.84 (0.05 to 16.9, 83) in cerebellum, 1.25 (0.02 to 11.1, 77) in spinal cord and 1.32 (0.13 to 15.2, 39) in brain stem. Total Hg concentrations in the cerebellum increased with age (p<0.05). Between 35 and 45% of HgT was water-soluble, of which, 32 to 41% was methyl mercury (MeHg) and 59 to 68% was labile inorganic Hg. The concentration of MeHg (range: 0.03 to 1.05 mg kg(-1) ww) was positively associated with HgT concentration, and the percent MeHg (4 to 109%) decreased exponentially with increasing HgT concentration in the spinal cord, cerebellum, frontal lobe and temporal lobe. There was a positive association between SeT and HgT in all brain regions (p<0.05) suggesting that Se may play a role in the detoxification of Hg in the brain. The concentration of HgT in the cerebellum was significantly associated with HgT in other organs. Therefore, HgT concentrations in organs that are frequently sampled in bio-monitoring studies could be used to estimate HgT concentrations in the cerebellum, which is the target organ of MeHg toxicity.

Methylmercury and selenium speciation in different tissues of beluga whales (Delphinapterus leucas) from the western Canadian Arctic.

Monitoring data have shown that the total monomethylmercury (CH(3) Hg(+) and its complexes; collectively referred as MeHg hereafter) concentrations in Arctic marine mammals have remained very high in recent decades. Toward a better understanding of the metabolic and toxicological implications of these high levels of MeHg, we report here on the molecular forms of MeHg in the muscle, brain, liver, and kidneys of 10 beluga whales from the western Canadian Arctic. In all tissues analyzed, monomethylmercury was found to be dominated by methylmercuric cysteinate, a specific form of MeHg believed to be able to transport across the blood-brain barrier. Another MeHg-thiol complex, methylmercuric glutathionate, was also detected in the muscle and, to a much lesser extent, in the liver and brain tissues. Furthermore, a profound inorganic Hg peak was detected in the liver and brain tissues, which showed the same retention time as a selenium (Se) peak, suggesting the presence of an Hg-Se complex, most likely an inorganic Hg complex with a selenoamino acid. These results provide the first analytical support that the binding of MeHg with glutathione and Se may have protected beluga whales from the toxic effect of high concentrations of MeHg in their body.

Historic dietary exposure to perfluorooctane sulfonate, perfluorinated carboxylates, and fluorotelomer unsaturated carboxylates from the consumption of store-bought and restaurant foods for the Canadian population.

Perfluorinated compounds (PFCs) have been detected in humans worldwide and are of health concern. This study measured the concentration of PFCs in composite samples collected for the 1998 Health Canada Total Diet Study and estimated dietary exposure for the Canadian population (older than 12 years of age) using previously collected dietary data (n = 1721). PFCs were detected in 8 samples including processed meats, preprepared foods, and peppers with a range of concentrations from 0.48 to 5.01 ng g(-1) (wet weight). 6:2 fluorotelomer unsaturated carboxylate (FTUCA) was detected in cold cuts at a concentration of 1.26 ng g(-1). Mean daily PFC exposure estimates ranged from 1.5 to 2.5 ng (kg of body weight)(-1). Perfluorinated carboxylates (PFCA C(7)-C(11)) contributed more to PFC exposure than either perfluorooctane sulfonate (PFOS) or FTUCA. Total PFCAs in cakes and cookies, lunchmeats, and green vegetables were the main contributors to dietary exposure, although these exposure levels were below the provisional tolerable daily intake provided by the German Drinking Water Commission. Dietary exposure to total PFCs has not changed over time, although the contribution of PFOS to total PFC exposure may have increased between 1998 and 2004. Further research on the sources of contamination of processed and preprepared foods is required. Dietary exposure to PFCs among Canadians poses minimal health risks based on current toxicological information.

Estimated dietary exposure to fluorinated compounds from traditional foods among Inuit in Nunavut, Canada.

Increasing evidence shows that persistent organic pollutants such as perfluorinated compounds (PFCs) are found in the Arctic ecosystem and their prevalence is causing human health concerns. The objective of this study was to estimate dietary exposure to PFCs among Inuit in northern Canada. Perfluorooctane sulfonate (PFOS), perfluorinated carboxylates (PFCA C(7)-C(11)) and fluorotelomer unsaturated carboxylic acids (6:2, 8:2 and 10:2 FTUCA) were measured in 68 traditional foods collected in Nunavut between 1997 and 1999. Total PFC concentrations were highest in caribou liver (mean+/-standard deviation; 6.2+/-5.5 ng g(-1)), ringed seal liver (minimum, maximum; 7.7, 10.2 ng g(-1)), polar bear meat (7.0 ng g(-1)), and beluga meat (minimum, maximum; 7.0, 5.8 ng g(-1)). Inuit food intake data from 24-h recalls conducted in Nunavut between 1997 and 1999 were used for the calculation of PFC exposure. Mean daily dietary exposure was calculated to range from 210 to 610 ng person(-1) (0.6-8.5 ng kg body weight(-1)) for 754 individuals. Dietary exposure to PFCs was statistically significantly higher in men in the 41-60 year age group (p<0.05) than younger men (<40 years old) and women from the same age group. Traditional foods contributed a higher percentage to PFC exposure than market foods in all age and gender groups. Caribou meat contributed 43-75% of daily PFC dietary exposure. Health risks associated with these estimated exposure levels are minimal based on current toxicological information available from animal feeding studies. However, it is important to monitor the concentrations of PFCs in key food items given that PFCA levels have been found to be increasing in the Canadian Arctic.