Chlorinated hydrocarbon contaminants and metabolites in polar bears (Ursus maritimus) from Alaska, Canada, East Greenland, and Svalbard: 1996-2002.

A suite of chlorinated hydrocarbon contaminants (CHCs) including organochlorine pesticides (OCPs) and by-products, polychlorinated biphenyls (PCBs), and methyl sulfone (MeSO2) PCB and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) metabolites were determined in adipose tissue of 107 adult and sub-adult polar bears, almost exclusively females, sampled between 1996 and 2002 from populations spanning Arctic and Subarctic regions of Alaska, Canada, East Greenland, and Svalbard. The East Greenland and Svalbard populations of polar bears were distinguished by higher proportions of dichlorodiphenyldichloroethane (DDT)-related compounds, nonachlors, oxychlordane, and higher-chlorinated and persistent PCB congeners (hepta- to nona-chlorinated). Conversely, Alaska, the westernmost population of the North American Arctic, was characterized by higher proportions of relatively volatile compounds such as hexachlorocyclohexanes (HCHs) and pentachlorobenzene (PnCBz), lower-chlorinated PCB congeners (tri- to penta-chlorinated), and lower proportions of oxychlordane. Geometric mean (GM) with 95% confidence limits (CL) SigmaHCH concentrations were highest in Alaska male polar bear fat samples (GM 593; CL 363-909 ng g-1 lipid weight), SigmaDDT concentration were highest in East Greenland female samples (GM 309; CL 249-490 ng g-1 l.w.), and Sigma42PCB (GM 5972; CL 4637-9129 ng g-1 l.w.) and SigmaMeSO2-PCB (GM 198; CL 162-279 ng g-1 l.w.) concentrations were highest in female samples collected from Svalbard. The distribution of Sigma-chlordane-related compounds (SigmaCHL), SigmaCBz, mirex, and dieldrin was relatively uniform among the populations of polar bears investigated. The present 1996-2002 data of female polar bear fat samples was compared to spatial assessments of female polar bear fat samples collected between 1989 and 1993 from comparable populations. The two-point temporal comparisons showed a general decrease for age-adjusted mean concentrations of SigmaCHL, p,p'-DDE, Sigma42PCB, SigmaMeSO2-PCB and 3-MeSO2-p,p'-DDE over a period of approximately 10 years. However, concentrations of dieldrin were comparatively unchanged. Comparisons of present 2001-2002 concentrations in fat of female polar bears from Western Hudson Bay showed great consistency with temporal trends (1991-1999) previously reported for the same region, i.e. the apparent non-decreasing trend of SigmaCHL, beta-HCH, SigmaHCH and dieldrin, and the apparent declining trend for SigmaPCB. However, present concentrations of alpha-HCH and SigmaCBz were elevated, and SigmaDDT was notably lower in Western Hudson Bay samples compared to the last measurements in fat samples collected in 1999, which was not in accord with reported temporal trends for this region. As a result of their relatively high degree of contamination, East Greenland and Svalbard polar bears are at higher health risk of contaminant exposure among Arctic and Subarctic populations. In addition to continued biomonitoring, further research on health and population status is needed to evaluate the impact from chronic exposure of polar bear populations to CHCs and their metabolites.

Temporal trends of perfluoroalkyl contaminants in polar bears (Ursus maritimus) from two locations in the North American Arctic, 1972-2002.

Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.

Brominated flame retardants in polar bears (Ursus maritimus) from Alaska, the Canadian Arctic, East Greenland, and Svalbard.

Polybrominated diphenyl ethers (PBDEs) were determined in adipose tissue of adult and subadult female polar bears sampled between 1999 and 2002 from sub-populations in Arctic Canada, eastern Greenland, and Svalbard, and in males and females collected from 1994 to 2002 in northwestern Alaska. Only 4 congeners (BDE47, 99, 100, and 153) were consistently identified in all samples. BDE47 was the major PBDE congener representing from 65% to 82% of the sum (sigma) PBDEs. Age was not a significant covariate for individual PBDEs or sigmaPBDE. Higher proportions of BDE 99, 100, and 153 were generally found in samples from the Canadian Arctic than from Svalbard or the Bering-Chukchi Sea area of Alaska. Geometric mean sigmaPBDE concentrations were highest for female polar bear fat samples collected from Svalbard (50 ng/g lipid weight (lw)) and East Greenland (70 ng/g lw). Significantly lower sigmaPBDE concentrations were found in fat of bears from Canada and Alaska (means ranging from 7.6 to 22 ng/g lw).

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus).

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.