(Table 2) Mercury and selenium concentration in the brain stem of wild polar bears (Ursus maritimus), east Greenland

Polar bears (Ursus maritimus) are exposed to high concentrations of mercury because they are apex predators in the Arctic ecosystem. Although mercury is a potent neurotoxic heavy metal, it is not known whether current exposures are of neurotoxicological concern to polar bears. We tested the hypotheses that polar bears accumulate levels of mercury in their brains that exceed the estimated lowest observable adverse effect level (20 µg/g dry wt) for mammalian wildlife and that such exposures are associated with subtle neurological damage, as determined by measuring neurochemical biomarkers previously shown to be disrupted by mercury in other high-trophic wildlife. Brain stem (medulla oblongata) tissues from 82 polar bears subsistence hunted in East Greenland were studied. Despite surprisingly low levels of mercury in the brain stem region (total mercury = 0.36 ± 0.12 µg/g dry wt), a significant negative correlation was measured between N-methyl-D-aspartate (NMDA) receptor levels and both total mercury (r = -0.34, p < 0.01) and methylmercury (r = -0.89, p < 0.05). No relationships were observed among mercury, selenium, and several other neurochemical biomarkers (dopamine-2, gamma-aminobutyric acid type A, muscarinic cholinergic, and nicotinic cholinergic receptors; cholinesterase and monoamine oxidase enzymes). These data show that East Greenland polar bears do not accumulate high levels of mercury in their brain stems. However, decreased levels of NMDA receptors could be one of the most sensitive indicators of mercury's subclinical and early effects.

(Table 1) Concentrations of neutral and phenolic organohalogen compounds in adipose tissue, blood, brain and liver of polar bears (Ursus maritimus) from East Greenland

The tissue-specific composition of sum classes of brominated and chlorinated contaminants and metabolic/degradation byproducts was determined in adult male and female polar bears from East Greenland. Significantly (p < 0.05) higher concentrations of SUM-PCBs, various other organochlorines such as SUM-CHL, p,p'-DDE, SUM-CBz, SUM-HCHs, octachlorostyrene (OCS),SUM-mirex, dieldrin, the flame retardants SUM-PBDEs, and total-(R)-hexabromocyclododecane (HBCD), SUM-methylsulfonyl (MeSO2)-PCBs and 3-MeSO2-p,p'-DDE, were found in the adipose and liver tissues relative to whole blood and brain. In contrast, SUM-hydroxyl (OH)-PCB, 4-OH-heptachlorostyrene and SUM-OH-PBDE concentrations were significantly highest (p < 0.05) in whole blood, whereas the highest concentrations of SUM-OH-PBBs were found in the adipose tissue. Based on the total concentrations of all organohalogens in all three tissues and blood, the combined body burden was estimated to be 1.34 ± 0.12 g, where >91% of this amount was accounted for by the adipose tissue alone, followed by the liver, whole blood, and brain. These results show that factors such as protein association and lipid solubility appear to be differentially influencing the toxicokinetics, in terms of tissue composition/localization and burden, of organohalogen classes with respect to chemical structure and properties such as the type of halogenation (e.g., chlorination or bromination), and the presence or absence of additional phenyl group substituents (e.g., MeO and OH groups). The tissue- and blood-specific accumulation (or retention) among organohalogen classes indicates that exposure and any potential contaminant-mediated effects in these polar bears are likely tissue or blood specific.

(Tables 1,2) Tracking records and space use statistics of polar bears (Ursus maritimus) in Storfjorden, Svalbard

Arctic sea ice is declining rapidly, making it vital to understand the importance of different types of sea ice for ice-dependent species such as polar bears Ursus maritimus. In this study we used GPS telemetry (25 polar bear tracks obtained in Svalbard, Norway, during spring) and high-resolution synthetic aperture radar (SAR) sea-ice data to investigate fine-scale space use by female polar bears. Space use patterns differed according to reproductive state; females with cubs of the year (COYs) had smaller home ranges and used fast-ice areas more frequently than lone females. First-passage time (FPT) analysis revealed that females with COYs displayed significantly longer FPTs near (<10 km) glacier fronts than in other fast-ice areas; lone females also increased their FPTs in such areas, but they also frequently used drifting pack ice. These results clearly demonstrate the importance of fast-ice areas, in particular close to glacier fronts, especially for females with COYs. Access to abundant and predictable prey (ringed seal pups), energy conservation and reluctance to cross large open water areas are possible reasons for the observed patterns. However, glacier fronts are retracting in Svalbard, and declines in land-fast ice have been notable over the past decade. The eventual disappearance of these important habitats might become critical for the survival of polar bear cubs in Svalbard and other regions with similar habitat characteristics. Given the relatively small size of many fast-ice areas in Svalbard, the results observed in this study would not have been revealed using less accurate location data or lower-resolution sea-ice data.

Mercury content and isotopic composition of teeth, and sex and age of skulls of polar bears collected in Svalbard

We examined the use of mercury (Hg) and nitrogen and carbon stable isotopes in teeth of polar bear (Ursus maritimus) from Svalbard as biotracers of temporal changes in Hg pollution exposure between 1964 and 2003. Teeth were regarded as a good matrix of the Hg exposure, and in total 87 teeth of polar bears were analysed. Dental Hg levels ranged from 0.6 to 72.3 ng/g dry weight and increased with age during the first 10 years of life. A decreasing time trend in Hg concentrations was observed over the recent four decades while no temporal changes were found in the stable isotope ratios of nitrogen (d15N) and carbon (d13C). This suggests that the decrease of Hg concentrations over time was more likely due to a lower environmental Hg exposure in this region rather than a shift in the feeding habits of Svalbard polar bears.

(Table 1) Concentration of PCB and other contaminants in blood plasma of polar bears (Ursus maritimus) from Svalbard

Persistent chemicals accumulate in the arctic environment due to their chemical reactivity and physicochemical properties and polychlorinated biphenyls (PCBs) are the most concentrated pollutant class in polar bears (Ursus maritimus). Metabolism of PCB and polybrominated biphenyl ether (PBDE) flame-retardants alter their toxicological properties and these metabolites are known to interfere with the binding of thyroid hormone (TH) to transthyretin (TTR) in rodents and humans. In polar bear plasma samples no binding of [125I]-T4 to TTR was observed after incubation and PAGE separation. Incubation of the plasma samples with [14C]-4-OH-CB107, a compound with a higher binding affinity to TTR than the endogenous ligand T4 resulted in competitive binding as proven by the appearance of a radio labeled TTR peak in the gel. Plasma incubation with T4 up to 1 mM, a concentration that is not physiologically relevant anymore did not result in any visible competition. These results give evidence that the binding sites on TTR for T4 in wild living polar bears are completely saturated. Such saturation of binding sites can explain observed lowered levels of THs and could lead to contaminant transport into the developing fetus.

(Table S2) Biometric data, time of ice breakup and carbon isotopic composition of adipose tissue of polar bears (Ursus maritimus) between 1991-2007

Two global environmental issues, climate change and contamination by persistent organic pollutants, represent major concerns for arctic ecosystems. Yet, it is unclear how these two stressors interact in the Arctic. For instance, the influence of climate-associated changes in food web structure on exposure to pollutants within arctic ecosystems is presently unknown. Here, we report on recent changes in feeding ecology (1991-2007) in polar bears (Ursus maritimus) from the western Hudson Bay subpopulation that have resulted in increases in the tissue concentrations of several chlorinated and brominated contaminants. Differences in timing of the annual sea ice breakup explained a significant proportion of the diet variation among years. As expected from climate change predictions, this diet change was consistent with an increase in the consumed proportions of open water-associated seal species compared to ice-associated seal species in years of earlier sea ice breakup. Our results demonstrate that climate change is a modulating influence on contaminants in this polar bear subpopulation and may pose an additional and previously unidentified threat to northern ecosystems through altered exposures to contaminants.

(Table 2) Mercury concentration in hair of Northwest Greenland polar bears (Ursus maritimus)

Hair samples from 117 Northwest Greenland polar bears (Ursus maritimus) were taken during 1892-2008 and analyzed for total mercury (hereafter Hg). The sample represented 28 independent years and the aim of the study was to analyze for temporal Hg trends. Mercury concentrations showed yearly significant increases of 1.6-1.7% (p < 0.0001) from 1892 to 2008 and the two most recent median concentrations from 2006 and 2008 were 23- to 27-fold higher respectively than baseline level from 1300 A.D. in the same region (Nuullit). This indicates that the present (2006-2008) Northwest Greenland polar bear Hg exposure is 95.6-96.2% anthropogenic in its origin. Assuming a continued anthropogenic increase, this model estimated concentrations in 2050 and 2100 will be 40- and 92-fold the baseline concentration, respectively, which is equivalent to a 97.5 and 98.9% man-made contribution. None of the 2001-2008 concentrations of Hg in Northwest Greenland polar bear hair exceeded the general guideline values of 20-30 µg/g dry weight for terrestrial wildlife, whereas the neurochemical effect level of 5.4 µg Hg/g dry weight proposed for East Greenland polar bears was exceeded in 93.5% of the cases. These results call for detailed effect studies in main target organs such as brain, liver, kidney, and sexual organs in the Northwest Greenland polar bears.

Concentrations of brominated and chlorinated contaminants in adipose tissue of polar bears (Ursus maritimus) between 1991-2007

Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, sum DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); alpha-hexachlorocyclohexane (alpha-HCH) decreased (-11%/year); beta-HCH increased ( + 8.3%/year); and sum PCB and sum chlordane (CHL), both contaminants at highest concentrations in all years (>1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (-1.6%/year to -6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). sum chlorobenzene, octachlorostyrene, sum mirex, sum MeSO2-PCB and dieldrin did not significantly change. Increasing sum PBDE levels (+13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(alpha)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or "weathering" of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year. DDT patterns were not associated with any explanatory variables, possibly related to local DDT sources. Contaminant pattern trends may be useful in distinguishing the possible role of ecological/diet changes on contaminant burdens from expected dynamics due to atmospheric sources and weathering.