To better understand the bioaccumulation behavior of perfluoroalkyl contaminants (PFCs), we conducted a comparative analysis of PFCs and lipophilic organohalogens in a Canadian Arctic marine food web. Concentrations of perfluorooctane sulfonic acid (PFOS), perfluorooctansulfoamide (PFOSA), and C7-C14 perfluorocarboxylic acids (PFCAs) ranged between 0.01 and 0.1 ng x g(-1) dry wt in sediments and 0.1 and 40 ng x g(-1) wet wt in biota, which was equivalent to or higher than levels of PCBs, PBDEs, and organochlorine pesticides. In beluga whales, PFOS and PFCA concentrations were higher (P < 0.05) in protein-rich compartments (liver and blood), compared to other tissues/fluids (milk, blubber, muscle, and fetus). In the marine mammalian food web, concentrations of PFOSA and lipophilic organochlorines (ng x g(-1) lipid equivalent) and proteinophilic substances (i.e., PFOS and C8-C14 PFCAs, ng x g(-1) protein) increased significantly (P < 0.05) with trophic level. Trophic magnification factors (TMFs) of organochlorines ranged between 5 and 14 and exhibited significant curvilinear relationships (P < 0.05) with octanol-water and octanol-air partition coefficients (KOW, KOA). TMFs of perfluorinated acids (PFAs) ranged between 2 and 11 and exhibited similar correlation (P < 0.05) with protein-water and protein-air partition coefficients (KPW, KPA). PFAs did not biomagnify in the aquatic piscivorous food web (TMF range: 0.3-2). This food web specific biomagnification behavior was attributed to the high aqueous solubility and low volatility of PFAs. Specifically, the anticipated phase-partitioning of these proteinophilic substances, represented by their protein-water (KPW) and protein-air (KPA) partition coefficients, likely results in efficient respiratory elimination in water-respiring organisms but very slow elimination and biomagnification in air-breathing animals. Lastly, the results indicate that PFOS exposure in nursing Hudson Bay beluga whale calves (CI95 range = 2.7 x 10(-5) to 1.8 x 10(-4) mg x kg bw(-1) x d(-1)), exceedsthe oral reference dose for PFOS (7.5 x 10(-5) mg x kg bw(-1) x d(-1)), which raises concern for potential biological effects in these and other sensitive Arctic marine wildlife species.
Polybrominated diphenyl ethers (PBDEs) were found in water, surface sediments, and bivalve samples that were collected from the San Francisco Estuary in 2002. sigmaPBDE concentrations in water samples ranged from 3 to 513 pg/ L, with the highest concentrations found in the Lower South Bay (range 103-513 pg/L) region, which receives approximately 26% of the Estuary's wastewater treatment plant effluents. The sigmaPBDEs in sediments ranged from below detection limits to 212 ng/g dry wt, with the highest concentration found at a South Bay station (212 ng/g dry wt), which was up to 3 orders of magnitude higher than other stations. The sigmaPBDE concentrations ranged from 9 to 64 ng/g dry wt in oysters (Crassostrea gigas), from 13 to 47 ng/g dry wt in mussels (Mytilus californianus), and from 85 to 106 ng/g dry wt in clams (Corbicula fluminea). Only three PBDE congeners were detected in bivalves, BDE-47, BDE-99, and BOE-100; these are the most bioaccumulative congeners from the commercial Penta-BDE mixture.
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