Occurrence of emerging brominated flame retardants and organophosphate esters in marine wildlife from the Norwegian Arctic.

To understand the exposure and potential sources of emerging brominated flame retardants (EBFR) and organophosphate esters (OPEs) in marine wildlife from the Norwegian Arctic, we investigated concentrations of EBFRs in 157 tissue samples from nine species of marine vertebrates and OPEs in 34 samples from three whale species. The samples, collected from a wide range of species with contrasting areal use and diets, included blubber of blue whales, fin whales, humpback whales, white whales, killer whales, walruses and ringed seals and adipose tissue and plasma from polar bears, as well as adipose tissue from glaucous gulls. Tris(2-ethylhexyl) phosphate (TEHP) and tris(2-chloroisopropyl) phosphate (TCIPP) ranged from <0.61 to 164 and < 0.8-41 ng/g lipid weight, respectively, in blue whales and fin whales. All other EBRFs and OPEs were below the detection limit or detected only at low concentration. In addition to the baseline information on the occurrence of EBFRs and OPEs in marine wildlife from the Arctic, we provide an in-depth discussion regarding potential sources of the detected compounds. This information is important for future monitoring and management of EBFRs and OPEs.

A deep dive into fat: Investigating blubber lipidomic fingerprint of killer whales and humpback whales in northern Norway.

In cetaceans, blubber is the primary and largest lipid body reservoir. Our current understanding about lipid stores and uses in cetaceans is still limited, and most studies only focused on a single narrow snapshot of the lipidome. We documented an extended lipidomic fingerprint in two cetacean species present in northern Norway during wintertime. We were able to detect 817 molecular lipid species in blubber of killer whales (Orcinus orca) and humpback whales (Megaptera novaeangliae). The profiles were largely dominated by triradylglycerols in both species and, to a lesser extent, by other constituents including glycerophosphocholines, phosphosphingolipids, glycerophosphoethanolamines, and diradylglycerols. Through a unique combination of traditional statistical approaches, together with a novel bioinformatic tool (LION/web), we showed contrasting fingerprint composition between species. The higher content of triradylglycerols in humpback whales is necessary to fuel their upcoming half a year fasting and energy-demanding migration between feeding and breeding grounds. In adipocytes, we assume that the intense feeding rate of humpback whales prior to migration translates into an important accumulation of triacylglycerol content in lipid droplets. Upstream, the endoplasmic reticulum is operating at full capacity to supply acute lipid storage, consistent with the reported enrichment of glycerophosphocholines in humpback whales, major components of the endoplasmic reticulum. There was also an enrichment of membrane components, which translates into higher sphingolipid content in the lipidome of killer whales, potentially as a structural adaptation for their higher hydrodynamic performance. Finally, the presence of both lipid-enriched and lipid-depleted individuals within the killer whale population in Norway suggests dietary specialization, consistent with significant differences in δ15N and δ13C isotopic ratios in skin between the two groups, with higher values and a wider niche for the lipid-enriched individuals. Results suggest the lipid-depleted killer whales were herring specialists, while the lipid-enriched individuals might feed on both herrings and seals.

Expression of DNA repair genes in arctic char (Salvelinus alpinus) from Bjørnøya in the Norwegian Arctic.

High levels of organochlorines (OCs) have been measured in arctic char (Salvelinus alpinus) from Lake Ellasjøen on Bjørnøya, Norway (74.30°N, 19.0°E). In a nearby lake, Laksvatn, the OC-levels in arctic char were low. A previous study has shown that char from Ellasjøen had significantly higher levels of DNA double strand breaks (DSBs) than char from Lake Laksvatn. Even though there is increasing evidence of the genotoxic effects of OCs, little is known about the effects of OCs on the DNA repair system. The aim of the present study was to determine if the two main DNA DSB repair mechanisms, homologous recombination (HR) and non-homologous end-joining (NHEJ), are affected by the higher OC and DSB level in char from Ellasjøen. This was analysed by comparing the transcript level of 11 genes involved in DNA DSB repair in char liver samples from Ellasjøen (n = 9) with char from Laksvatn (n = 12). Six of the investigated genes were significantly upregulated in char from Ellasjøen. As the expression of DNA DSB repair genes was increased in the contaminant-exposed char, it is likely that the DNA DSB repair capacity is induced in these individuals. This induction was positively correlated with the DNA DSB and negatively correlated with one or several OCs for four of these genes. However, the strongest predictor variable for DNA repair genes was habitat, indicating genetic differences in repair capacity between populations. As char from Ellasjøen still had significantly higher levels of DSBs compared to char from Laksvatn, it is possible that chronic exposure to OCs and continued production of DSB has caused selective pressure within the population for fixation of adaptive alleles. It is also possible that DSB production was exceeding the repair capacity given the prevailing conditions, or that the OC or DSB level was above the threshold value of inhibition of the DNA repair system resulting in the rate of DNA damage exceeding the rate of repair.

Effects of the sea lice bath treatment pharmaceuticals hydrogen peroxide, azamethiphos and deltamethrin on egg-carrying shrimp (Pandalus borealis).

This study investigated effects of sea lice pharmaceuticals on egg-bearing deep-water shrimp (Pandalus borealis). Both mortality and sub-lethal effects (behavior, embryo development, and reproductive output) were studied for each of three pharmaceuticals alone and in different sequential combinations. The most severe effect was observed for deltamethrin where 2 h exposure to 330 times diluted treatment dose (alone and in sequential application with hydrogen peroxide and azamethiphos) induced almost 100% mortality within a few days after exposure. Similar effects were not observed for hydrogen peroxide or azamethiphos. However, sequential treatment of hydrogen peroxide and azamethiphos (2 h exposure to each pharmaceutical; 500 times dilution) resulted in >40% mortality during the first week following treatment. No sub-lethal effects or loss of eggs in female shrimp could be related to exposure to the bath treatments. Future studies should investigate potential sub-lethal effects at exposure concentrations close to the no-effect concentration.

The sensitivity of the deepsea species northern shrimp (Pandalus borealis) and the cold-water coral (Lophelia pertusa) to oil-associated aromatic compounds, dispersant, and Alaskan North Slope crude oil.

This study investigated the sensitivity of two deepsea species using mortality of northern shrimp (Pandalus borealis) and polyp activity of stony coral (Lophelia pertusa) to dispersant, Corexit 9500 and aromatic hydrocarbons (toluene, 2-methylnaphthalene, phenanthrene) in 96-h tests. Resulting hydrocarbon toxicity data were fit to the Target Lipid Model to generate predictive models and determine species sensitivity. Toxicity of chemically enhanced water accommodated fractions of Alaskan North Slope crude oil (ANS-oil) was also investigated with shrimp using nominal loading, total petroleum hydrocarbons and biomimetic extraction (BE) as oil exposure metrics. Coral were more sensitive to dispersant than shrimp while similar sensitivity was observed for hydrocarbons. Study and literature findings indicate deepsea species exhibit acute sensitivities to dispersant, hydrocarbons and oil that are comparable to pelagic species. Results support use of passive sampling methods to quantify dissolved oil for interpreting oil toxicity tests and suggest models for predicting time-dependence of toxicity warrant re-evaluation.

DNA Double-Strand Breaks in Arctic Char (Salvelinus alpinus) from Bjørnøya in the Norwegian Arctic.

High levels of organochlorine contaminants (OCs) have been found in arctic char (Salvelinus alpinus) from Lake Ellasjøen, Bjørnøya (Norwegian Arctic). The aim of the present study was to investigate the potential genotoxic effect of environmental organochlorine contaminant exposure in arctic char from Ellasjøen compared with arctic char from the low-contaminated Lake Laksvatn nearby. Blood was analyzed using agarose gel electrophoresis and image data analysis to quantify the fraction of total DNA that migrated into the gel (DNA-FTM) as a relative measure of DNA double-strand breaks (DSBs). Analysis by GC-MS of muscle samples showed an average 43 times higher concentration of ΣOCs in arctic char from Ellasjøen (n = 18) compared with Laksvatn char (n = 21). Char from Lake Ellasjøen had a much higher frequency of DSBs, as measured by DNA-FTM, than char from Lake Laksvatn. Principal component analysis and multiple linear regressions show that there was a significant positive relationship between DSBs and levels of organochlorine contaminants in the char. In addition, DSBs were less frequent in reproductively mature char than in immature char. The results suggest that organochlorine contaminants are genotoxic to arctic char. Environ Toxicol Chem 2019;38:2405-2413. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Underwater hyperspectral classification of deep sea corals exposed to 2-methylnaphthalene.

Coral reefs around the world are under threat due to anthropogenic impacts on the environment. It is therefore important to develop methods to monitor the status of the reefs and detect changes in the health condition of the corals at an early stage before severe damage occur. In this work, we evaluate underwater hyperspectral imaging as a method to detect changes in health status of both orange and white color morphs of the coral species Lophelia pertusa. Differing health status was achieved by exposing 60 coral samples to the toxic compound 2-methylnaphthalene in concentrations of 0 mg L-1 to 3.5 mg L-1. A machine learning model was utilized to classify corals according to lethal concentration (LC) levels LC5 (5% mortality) and LC25 (25% mortality), solely based on their reflectance spectra. All coral samples were classified to correct concentration group. This is a first step towards developing a remote sensing technique able to assess environmental impact on deep-water coral habitats over larger areas.

Temporal Trends of Persistent Organic Pollutants in Barents Sea Polar Bears ( Ursus maritimus) in Relation to Changes in Feeding Habits and Body Condition.

Temporal trends of persistent organic pollutants (POPs: PCBs, OH-PCBs, p, p'-DDE, HCB, ß-HCH, oxychlordane, BDE-47, and 153) in relation to changes in feeding habits and body condition in adult female polar bears ( Ursus maritimus) from the Barents Sea subpopulation were examined over 20 years (1997-2017). All 306 samples were collected in the spring (April). Both stable isotope values of nitrogen (δ15N) and carbon (δ13C) from red blood cells declined over time, with a steeper trend for δ13C between 2012 and 2017, indicating a decreasing intake of marine and high trophic level prey items. Body condition, based on morphometric measurements, had a nonsignificant decreasing tendency between 1997 and 2005, and increased significantly between 2005 and 2017. Plasma concentrations of BDE-153 and ß-HCH did not significantly change over time, whereas concentrations of Σ4PCB, Σ5OH-PCB, BDE-47, and oxychlordane declined linearly. Concentrations of p, p'-DDE and HCB, however, declined until 2012 and 2009, respectively, and increased thereafter. Changes in feeding habits and body condition did not significantly affect POP trends. The study indicates that changes in diet and body condition were not the primary driver of POPs in polar bears, but were controlled in large part by primary and/or secondary emissions of POPs.

Effects of biometrics, location and persistent organic pollutants on blood clinical-chemical parameters in polar bears (Ursus maritimus) from Svalbard, Norway.

In the present study, blood clinical-chemical parameters (BCCPs) were analysed in 20 female and 18 male Svalbard polar bears (Ursus maritimus) captured in spring 2007. The aim was to study how age, body condition (BC), biometrics, plasma lipid content and geographical location may confound the relationship between persistent organic pollutants (POPs) including PCBs, HCB, chlordanes, DDTs, HCHs, mirex and OH-PCBs and the concentrations of 12 specific BCCPs (hematocrit [HCT], hemoglobin [HB], aspartate aminotransferase [ASAT], alanine aminotransferase [ALAT], γ-glutamyltransferase [GGT], creatine kinase [CK], triglycerides [TG], cholesterol [CHOL], high-density lipoprotein [HDL], creatinine (CREA], urea, potassium (K]), and to investigate if any of these BCCPs may be applied as potential biomarkers for POP exposure in polar bears. Initial PCA and O-PLS modelling showed that age, lipids, BC and geographical location (longitude and latitude) were important parameters explaining BCCPs in females. Following subsequent partial correlation analyses correcting for age and lipids, multiple POPs in females were still significantly correlated with HCT and HDL (all p < 0.05). In males, age, BM, BC and longitude were important parameters explaining BCCPs. Following partial correlation analyses correcting for age, biometrics, lipids and longitude in males, multiple POPs were significantly correlated with HCT, ASAT, GGT and CHOL (all p < 0.05). In conclusion, several confounding parameters has to be taken into account when studying the relations between BCCPs and POPs in polar bears. When correcting for these, in particular HCT may be used as a simple cost-efficient biomarker of POP exposure in polar bears. Furthermore, decreasing HDL concentrations and increasing CHOL concentration with increasing POP concentrations may indicate responses related to increased risk of cardiovascular disease. We therefore suggest to further study POP exposure and lipidome response to increase knowledge of the risk of cardiometabolic syndrome in polar bears.

The sensitivity of a deep-sea fish species (Anoplopoma fimbria) to oil-associated aromatic compounds, dispersant, and Alaskan North Slope crude oil.

A predominant concern following oil spills is toxicity to aquatic organisms. However, few data are available on effects in deep-sea cold water fishes. The present study had 3 major objectives. The first was to investigate the relative sensitivity of the deep-sea species Anoplopoma fimbria (sablefish) to acute effects of 3 aromatic compounds (toluene, 2-methylnaphthalene, and phenanthrene), dispersant alone, and chemically enhanced water accommodated fractions (CEWAFs) of Alaskan North Slope crude oil. The second was to determine the critical target lipid body burden (CTLBB) for sablefish by fitting aromatic hydrocarbon toxicity data to the target lipid model (TLM), which then allowed expression of CEWAF exposures in terms of dissolved oil toxic units. The final aim was to apply a passive sampling method that targets bioavailable, dissolved hydrocarbons as an alternative analytical technique for improved CEWAF exposure assessment. The results indicate that sablefish exhibit sensitivity to Corexit 9500 (96-h median lethal concentration [LC50] = 72.2 mg/L) within the range reported for other fish species. However, the acute CTLBB of 39.4 ± 2.1 µmol/goctanol lies at the lower end of the sensitivity range established for aquatic species. The utility of both toxic units and passive sampling measurements for describing observed toxicity of dispersed oil is discussed. The present study is novel in that a new test species is investigated to address the uncertainty regarding the sensitivity of deep-sea fishes, while also employing modeling and measurements to improve exposure characterization in oil toxicity tests. Environ Toxicol Chem 2018;37:2210-2221. © 2018 SETAC.

Choose Your Poison-Space-Use Strategy Influences Pollutant Exposure in Barents Sea Polar Bears.

Variation in space-use is common within mammal populations. In polar bears, Ursus maritimus, some individuals follow the sea ice (offshore bears) whereas others remain nearshore yearlong (coastal bears). We studied pollutant exposure in relation to space-use patterns (offshore vs coastal) in adult female polar bears from the Barents Sea equipped with satellite collars (2000-2014, n = 152). First, we examined the differences in home range (HR) size and position, body condition, and diet proxies (nitrogen and carbon stable isotopes, n = 116) between offshore and coastal space-use. Second, we investigated how HR, space-use, body condition, and diet were related to plasma concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) ( n = 113), perfluoroalkyl substances (PFASs; n = 92), and hydroxylated-PCBs ( n = 109). Offshore females were in better condition and had a more specialized diet than did coastal females. PCBs, OCPs, and hydroxylated-PCB concentrations were not related to space-use strategy, yet PCB concentrations increased with increasing latitude, and hydroxylated-PCB concentrations were positively related to HR size. PFAS concentrations were 30-35% higher in offshore bears compared to coastal bears and also increased eastward. On the basis of the results we conclude that space-use of Barents Sea female polar bears influences their pollutant exposure, in particular plasma concentrations of PFAS.

Characterizing cytotoxic and estrogenic activity of Arctic char tissue extracts in primary Arctic char hepatocytes.

Contaminants from various anthropogenic activities are detected in the Arctic due to long-range atmospheric transport, ocean currents, and living organisms such as migrating fish or seabirds. Although levels of persistent organic pollutants (POPs) in Arctic fish are generally low, local hot spots of contamination were found in freshwater systems such as Lake Ellasjøen at Bjørnøya (Bear Island, Norway). Higher concentrations of organic halogenated compounds (OHC), and higher levels of cytochrome P450 and DNA-double strand breaks were reported in Arctic char (Salvelinus alpinus) from this lake compared to fish from other lakes on Bjørnøya. Although several of the measured contaminants are potential endocrine disrupters, few studies have investigated potential endocrine disruptive effects of the contaminant cocktail in this fish population. The aim of this study was to compare acutely toxic and estrogenic potency of the cocktail of pollutants as evidenced by cytotoxic and/or estrogenic effects in vitro using extracts of Arctic char livers from contaminated Lake Ellasjøen with those from less contaminated Lake Laksvatn at Bjørnøya. This was performed by in situ sampling and contaminant extraction from liver tissue, followed by chemical analysis and in vitro testing of the following contaminated tissue extracts: F1-nonpolar OHC, F2-polar pesticides and metabolites of OHC, and F3-polar OHC. Contaminant levels were highest in extracts from Ellasjøen fish. The F2 and F3 extracts from Lake Laksvatn and Lake Ellasjøen fish reduced in vitro cell viability at a concentration ratio of 0.03-1 relative to tissue concentration in Arctic char. Only the F3 liver extract from Ellasjøen fish increased in vitro vitellogenin protein expression. Although compounds such as estrogenic OH-PCBs were quantified in Ellasjøen F3 extracts, it remains to be determined which compounds were inducing estrogenic effects.

Relationships between POPs, biometrics and circulating steroids in male polar bears (Ursus maritimus) from Svalbard.

The aim of this study was to determine the effects of persistent organic pollutants (POPs) and biometric variables on circulating levels of steroid hormones (androgens, estrogens and progestagens) in male polar bears (Ursus maritimus) from Svalbard, Norway (n = 23). Levels of pregnenolone (PRE), progesterone (PRO), androstenedione (AN), dehydroepiandrosterone (DHEA), testosterone (TS), dihydrotestosterone (DHT), estrone (E1), 17α-estradiol (αE2) and 17ß-estradiol (ßE2) were quantified in polar bear serum by gas chromatography tandem mass spectrometry (GC-MS/MS), while POPs were measured in plasma. Subsequently, associations between hormone concentrations (9 steroids), POPs (21 polychlorinated biphenyls (PCBs), 8 OH-PCBs, 8 organochlorine pesticides (OCPs) and OCP metabolites, and 2 polybrominated diphenyl ethers (PBDEs)) and biological variables (age, head length, body mass, girth, body condition index), capture date, location (latitude and longitude), lipid content and cholesterol levels were examined using principal component analysis (PCA) and orthogonal projections to latent structures (OPLS) modelling. Average concentrations of androgens, estrogens and progestagens were in the range of 0.57-83.7 (0.57-12.4 for subadults, 1.02-83.7 for adults), 0.09-2.69 and 0.57-2.44 nmol/L, respectively. The steroid profiles suggest that sex steroids were mainly synthesized through the Δ-4 pathway in male polar bears. The ratio between androgens and estrogens significantly depended on sexual maturity with androgen/estrogen ratios being approximately 60 times higher in adult males than in subadult males. PCA plots and OPLS models indicated that TS was positively related to biometrics, such as body condition index in male polar bears. A negative relationship was also observed between POPs and DHT. Consequently, POPs and body condition may potentially affect the endocrinological function of steroids, including development of reproductive tissues and sex organs and the general condition of male polar bears.

Hydroxylated polychlorinated biphenyls decrease circulating steroids in female polar bears (Ursus maritimus).

As a top predator in the Arctic food chain, polar bears (Ursus maritimus) are exposed to high levels of persistent organic pollutants (POPs). Because several of these compounds have been reported to alter endocrine pathways, such as the steroidogenesis, potential disruption of the sex steroid synthesis by POPs may cause implications for reproduction by interfering with ovulation, implantation and fertility. Blood samples were collected from 15 female polar bears in Svalbard (Norway) in April 2008. The concentrations of nine circulating steroid hormones; dehydroepiandrosterone (DHEA), androstenedione (AN), testosterone (TS), dihydrotestosterone (DHT), estrone (E1), 17α-estradiol (αE2), 17ß-estradiol (ßE2), pregnenolone (PRE) and progesterone (PRO) were determined. The aim of the study was to investigate associations among circulating levels of specific POP compounds and POP-metabolites (hydroxylated PCBs [OH-PCBs] and hydroxylated PBDEs [OH-PBDEs]), steroid hormones, biological and capture variables in female polar bears. Inverse correlations were found between circulating levels of PRE and AN, and circulating levels of OH-PCBs. There were no significant relationships between the steroid concentrations and other analyzed POPs or the variables capture date and capture location (latitude and longitude), lipid content, condition and body mass. Although statistical associations do not necessarily represent direct cause-effect relationships, the present study indicate that OH-PCBs may affect the circulating levels of AN and PRE in female polar bears and that OH-PCBs thus may interfere with the steroid homeostasis. Increase in PRO and a decrease in AN concentrations suggest that the enzyme CYP17 may be a potential target for OH-PCBs. In combination with natural stressors, ongoing climate change and contaminant exposure, it is possible that OH-PCBs may disturb the reproductive potential of polar bears.

Effect-directed analysis to explore the polar bear exposome: identification of thyroid hormone disrupting compounds in plasma.

Compounds with transthyretin (TTR)-binding potency in the blood plasma of polar bear cubs were identified with effect-directed analysis (EDA). This approach contributes to the understanding of the thyroid disrupting exposome of polar bears. The selection of these samples for in-depth EDA was based on the difference between the observed TTR-binding potency on the one hand and the calculated potency (based on known concentrations of TTR-binding compounds and their relative potencies) on the other. A library-based identification was applied to the liquid chromatography-time-of-flight-mass spectrometry (LC-ToF-MS) data by screening for matches between compound lists and the LC-ToF-MS data regarding accurate mass and isotope pattern. Then, isotope cluster analysis (ICA) was applied to the LC-ToF-MS data allowing specific screening for halogen isotope patterns. The presence of linear and branched nonylphenol (NP) was observed for the first time in polar bears. Furthermore, the presence of one di- and two monohydroxylated octachlorinated biphenyls (octaCBs) was revealed in the extracts. Linear and branched NP, 4'-OH-CB201 and 4,4'-OH-CB202 could be successfully confirmed with respect to their retention time in the analytical system. In addition, branched NP, mono- and dihydroxylated-octaCBs showed TTR-binding potencies and could explain another 32 ± 2% of the total measured activities in the extracts.

Transthyretin-binding activity of contaminants in blood from polar bear (Ursus maritimus) cubs.

We determined the transthyretin (TTR)-binding activity of blood-accumulating contaminants in blood plasma samples of approximately 4-months-old polar bear (Ursus maritimus) cubs from Svalbard sampled in 1998 and 2008. The TTR-binding activity was measured as thyroxine (T4)-like equivalents (T4-EQMeas). Our findings show that the TTR-binding activity related to contaminant levels was significantly lower (45%) in 2008 than in 1998 (mean ± standard error of mean: 1998, 2265 ± 231 nM; 2008, 1258 ± 170 nM). Although we cannot exclude a potential influence of between-year differences in capture location and cub body mass, our findings most likely reflect reductions of TTR-binding contaminants or their precursors in the arctic environment (e.g., polychlorinated biphenyls [PCBs]). The measured TTR-binding activity correlated positively with the cubs' plasma levels of hydroxylated PCBs (OH-PCBs). No such association was found between TTR-binding activity and the plasma levels of perfluoroalkyl substances (PFASs). The OH-PCBs explained 60 ± 7% and 54 ± 4% of the TTR-binding activity in 1998 and 2008, respectively, and PFASs explained ≤1.2% both years. Still, almost half the TTR-binding activity could not be explained by the contaminants we examined. The considerable levels of TTR-binding contaminants warrant further effect directed analysis (EDA) to identify the contaminants responsible for the unexplained part of the observed TTR-binding activity.

Perfluoroalkyl substances in polar bear mother-cub pairs: a comparative study based on plasma levels from 1998 and 2008.

Perfluoroalkyl substances (PFASs) are protein-binding blood-accumulating contaminants that may have detrimental toxicological effects on the early phases of mammalian development. To enable an evaluation of the potential health risks of PFAS exposure for polar bears (Ursus maritimus), an exposure assessment was made by examining plasma levels of PFASs in polar bear mothers in relation to their suckling cubs-of-the-year (~4 months old). Samples were collected at Svalbard in 1998 and 2008, and we investigated the between-year differences in levels of PFASs. Seven perfluorinated carboxylic acids (∑7PFCAs: PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA) and two perfluorinated sulfonic acids (∑2PFSAs: PFHxS and PFOS) were detected in the majority of the mothers and cubs from both years. In mothers and cubs, most PFCAs were detected in higher concentrations in 2008 than in 1998. On the contrary, levels of PFOS were lower in 2008 than in 1998, while levels of PFHxS did not differ between the two sampling years. PFOS was the dominating compound in mothers and cubs both in 1998 and in 2008. Concentration of PFHpA did not differ between mothers and cubs, while concentrations of PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA, PFHxS, and PFOS were higher in mothers than in their cubs. Except from PFHpA, all compounds correlated significantly between mothers and their cubs. The mean cub to mother ratios ranged from 0.15 for PFNA to 1.69 for PFHpA. On average (mean±standard error of mean), the levels of ∑7PFCAs and ∑2PFSAs in cubs were 0.24±0.01 and 0.22±0.01 times the levels in their mothers, respectively. Although maternal transfer appears to be a substantial source of exposure for the cubs, the low cub to mother ratios indicate that maternal transfer of PFASs in polar bears is relatively low in comparison with hydrophobic contaminants (e.g. PCBs). Because the level of several PFASs in mothers and cubs from both sampling years exceeded the levels associated with health effects in humans, our findings raise concern on the potential health effects of PFASs in polar bears from Svalbard. Effort should be made to examine the potential health effects of PFASs in polar bears.

PCBs and OH-PCBs in polar bear mother-cub pairs: a comparative study based on plasma levels in 1998 and 2008.

The aim of this study was to examine the plasma concentrations and prevalence of polychlorinated biphenyls (PCBs) and hydroxylated PCB-metabolites (OH-PCBs) in polar bear (Ursus maritimus) mothers (n=26) and their 4 months old cubs-of-the-year (n=38) from Svalbard to gain insight into the mother-cub transfer, biotransformation and to evaluate the health risk associated with the exposure to these contaminants. As samplings were performed in 1997/1998 and 2008, we further investigated the differences in levels and pattern of PCBs between the two sampling years. The plasma concentrations of Σ(21)PCBs (1997/1998: 5710 ± 3090 ng/g lipid weight [lw], 2008: 2560 ± 1500 ng/g lw) and Σ(6)OH-PCBs (1997/1998: 228 ± 60 ng/g wet weight [ww], 2008: 80 ± 38 ng/g ww) in mothers were significantly lower in 2008 compared to in 1997/1998. In cubs, the plasma concentrations of Σ(21)PCBs (1997/1998: 14680 ± 5350 ng/g lw, 2008: 6070 ± 2590 ng/g lw) and Σ(6)OH-PCBs (1997/1998: 98 ± 23 ng/g ww, 2008: 49 ± 21 ng/g ww) were also significantly lower in 2008 than in 1997/1998. Σ(21)PCBs in cubs was 2.7 ± 0.7 times higher than in their mothers. This is due to a significant maternal transfer of these contaminants. In contrast, Σ(6)OH-PCBs in cubs were approximately 0.53 ± 0.16 times the concentration in their mothers. This indicates a lower maternal transfer of OH-PCBs compared to PCBs. The majority of the metabolite/precursor-ratios were lower in cubs compared to mothers. This may indicate that cubs have a lower endogenous capacity to biotransform PCBs to OH-PCBs than polar bear mothers. Exposure to PCBs and OH-PCBs is a potential health risk for polar bears, and the levels of PCBs and OH-PCBs in cubs from 2008 were still above levels associated with health effects in humans and wildlife.

Blood plasma sample preparation method for the assessment of thyroid hormone-disrupting potency in effect-directed analysis.

A sample preparation method combining solid-phase extraction (SPE) and liquid-liquid extraction (LLE) was developed to be used in Effect-Directed Analysis (EDA) of blood plasma. Until now such a method was not available. It can be used for extraction of a broad range of thyroid hormone (TH)-disruptors from plasma with high recoveries. Validation of the method using spiked cow plasma showed good recoveries for hydroxylated polybrominated diphenyl ethers (OH-PBDEs; 93.8 ± 19.5%), hydroxylated polychlorinated biphenyls (OH-PCBs; 93.8 ± 15.5%), other halogenated phenols (OHPs; 107 ± 8.1%), and for short-chain (<8 C-atoms) perfluoroalkyl substances (PFASs; 85.2 ± 24.6%). In the same extracts, the potency of the compound classes spiked to the cow plasma to competitively bind to transthyretin (TTR) was recovered by 84.9 ± 8.8%. Furthermore, the SPE-LLE method efficiently removed endogenous THs from the extracts, thereby eliminating their possible contribution to the binding assay response. The SPE-LLE method was applied to polar bear plasma samples to investigate its applicability in future EDA studies focusing on TH-disrupting compounds in this top predator species that is exposed to relatively high levels of bioaccumulating pollutants. A first screening revealed TTR-binding potency in the polar bear plasma extracts, which could be explained for 60-85% by the presence of OH-PCBs.

Brominated flame retardants in North-East Atlantic marine ecosystems.

BACKGROUND: Concentrations of brominated flame retardants (BFRs) are reported to increase in marine ecosystems. OBJECTIVES: Characterize exposure to BFRs in animals from different trophic levels in North-East Atlantic coastal marine ecosystems along a latitudinal gradient from southern Norway to Spitsbergen, Svalbard, in the Arctic. Calanoid species were collected from the Oslofjord (59 degrees N), Froan (64 degrees N), and Spitsbergen (> 78 degrees N); Atlantic cod (Gadus morhua) from the Oslofjord and Froan; polar cod (Boreogadus saida) from Bear Island (74 degrees N) and Spitsbergen; harbor seal (Phoca vitulina) from the Oslofjord, Froan, and Spitsbergen; and ringed seal (Phoca vitulina) from Spitsbergen. Eggs of common tern (Sterna hirundo) were collected from the Oslofjord, and eggs of arctic terns (Sterna paradisaea) from Froan and Spitsbergen. RESULTS: Levels of polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD) generally decreased as a function of increasing latitude, reflecting distance from release sources. The clear latitudinal decrease in levels of BFRs was not pronounced in the two tern species, most likely because they are exposed during migration. The decabrominated compound BDE-209 was detected in animals from all three ecosystems, and the highest levels were found in arctic tern eggs from Spitsbergen. HBCD was found in animals from all trophic levels, except for in calanoids at Froan and Spitsbergen. CONCLUSIONS: Even though the levels of PBDEs and HBCD are generally low in North-East Atlantic coastal marine ecosystems, there are concerns about the relatively high presence of BDE-209 and HBCD.