Bioaccumulation of polybrominated diphenyl ethers and hexabromocyclododecane in the northwest Atlantic marine food web.

Seven species of teleost fishes comprising major prey of northwest Atlantic harbor seals were analyzed for polybrominated diphenyl ethers (PBDEs). PBDE concentrations in whole fish samples (n=87) were compared with those measured previously in harbor seal blubber to evaluate the transfer of PBDEs from prey to predator. Hexabromocyclododecane (HBCD) concentrations were measured in three fish species to provide an initial estimation of HBCD contamination in this ecosystem. HBCD was detected in 87% of the fish samples at concentrations ranging from 2.4 to 38.1 ng/g, lw (overall mean 17.2+/-10.2 ng/g, lw). SigmaPBDE concentrations in fish ranged from 17.9 to 94 ng/g, lw (overall mean 62+/-34 ng/g, lw). SigmaPBDE concentrations in the harbor seals were two orders of magnitude higher than levels in the fish. Biomagnification factors (BMFs) from fish to seals averaged from 17 to 76, indicating that tetra- to hexa-BDEs are highly biomagnified in this marine food web. BDE-47 was the dominant congener in all samples, suggesting exposure to the penta-BDE mixture. The presence of higher brominated congeners including BDE-209 at measurable levels in fish and seal tissue, along with the very high biomagnification of BDE-153, as well as -155, and -154, suggests recent exposure to the octa- and deca-BDE formulations in this US coastal marine food web, as well as the additional contribution of BDE-209 debromination in fish to the loading of persistent PBDEs in the seals. This is the first study to report the occurrence of BDE-209 and other higher BDEs in commercially important marine fishes from the northwest Atlantic.

Specific accumulation of perfluorochemicals in harbor seals (Phoca vitulina concolor) from the northwest Atlantic.

Concentrations of perfluorochemicals (PFCs) including perfluoroalkylsulfonates (PFSAs), and perfluoroalkylcarboxylates (PFCAs) were determined in liver of harbor seals (n=68) collected from the northwest Atlantic between 2000 and 2007. Of ten PFCs measured, perfluorooctane sulfonate (PFOS) concentrations were the highest in liver (8-1388 ng/g, ww), followed by perfluoroundecanoic acid (PFUnDA) (<1-30.7 ng/g, ww). An unusual accumulation profile of long-chain (C7-C12) PFCAs, and the predominance of PFUnDA, followed by PFNA in seal liver suggested that fluorotelomer alcohols (FTOHs) may be a major source of PFCAs in the northwest Atlantic. No gender-related differences in the concentrations of individual PFCs or total PFCs were found. Concentrations of PFOS and PFDS were higher in tissues of the pups than the adults, whereas concentrations of the PFCAs were similar between pups and adults. PFOS concentrations in the pups were 2.6-fold higher than those in the adult females, suggesting the importance of maternal transfer of PFCs. Hepatic PFOS concentrations were strongly, positively correlated with PFOSA, PFDS and individual PFCAs, indicating that harbor seals are exposed simultaneously to these compounds. Temporal comparisons of hepatic PFC concentrations showed a marginal increase of PFOS and PFCAs in the adult seals from 2000 to 2007. Unlike the spatial trend observed for polychlorinated biphenyls (PCBs), no south to north (urban-rural-remote) decreasing trend was observed for PFCs, suggesting the presence of diffuse sources of PFC contamination throughout the northwest Atlantic.

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic.

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. summation operatorPBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n=42) ranged from 80 to 25720 ng g(-1)lw, (overall mean 2403+/-5406 ng g(-1)lw). By age, mean summation operatorPBDE concentrations were: 3645+/-7388, 2945+/-5995, 1385+/-1265, and 326+/-193 ng g(-1)lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n=12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g(-1)lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.

Polybrominated diphenyl ethers (PBDEs) in farmed and wild salmon marketed in the Northeastern United States.

Recently, we reported on the analysis of polychlorinated biphenyls (PCBs) and chlorinated pesticides in farmed Atlantic salmon (Salmo salar) from Maine, eastern Canada, and Norway, and wild Alaskan Chinook salmon (Oncorhynchus tshawytscha). In this paper, we extend the analysis to polybrominated diphenyl ethers (PBDEs) in these samples. Total PBDE concentrations in the farmed salmon (0.4-1.4ng/g, wet weight, ww) were not significantly different from those in the wild Alaskan Chinook samples (0.4-1.2ng/g, ww), nor were significant differences found among regions. However, significant intra-regional variations in concentrations of total PBDEs and tetra-BDE 47 were observed in the salmon from the Canadian farms (p<0.01). Congener profiles were dominated by BDE-47, followed by the penta-BDEs 99 and 100. PBDE concentrations in the Canadian samples were lower than those reported two years earlier. Removal of skin resulted in no overall reduction in PBDE concentrations in our farmed salmon, and in some cases, PBDE concentrations were higher in skin-off samples. PBDEs were correlated with lipids only in the skinned samples, suggesting that there is greater accumulation and retention of PBDEs in muscle lipids than in skin-associated fat. In skin-on samples, modest correlations were observed between concentrations of PBDEs and PCBs (R(2)=0.47) and mono-ortho PCBs (R(2)=0.50), whereas PBDEs were not correlated with non-ortho PCBs.

PCBs, PCDD/Fs, and organochlorine pesticides in farmed Atlantic salmon from Maine, eastern Canada, and Norway, and wild salmon from Alaska.

Farmed Atlantic salmon (Salmo salar) from Maine and eastern Canada, wild Alaskan Chinook salmon (Oncorhynchus tshawytscha), and organically farmed Norwegian salmon samples were analyzed for the presence of polychlorinated biphenyls (PCBs), dioxin-like PCBs, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzo-p-furans (PCDFs), and chlorinated pesticides. PCDD and PCDF congeners were not detected in > 80% of the samples analyzed. Total PCB concentrations (7.2-29.5 ng/g, wet weight, ww) in the farmed salmon were significantly higher than those in the wild Alaskan Chinook samples (3.9-8.1 ng/g, ww). Concentrations of PCBs, WHO PCB TEQs, and chlorinated pesticides varied significantly by region. PCB and WHO PCB TEQ concentrations in farmed salmon from eastern Canada were lower than those reported in samples collected two years earlier, possibly reflecting recent industry efforts to lower contaminant concentrations in feed. Organically farmed Norwegian salmon had the highest concentrations of PCBs (mean: 27 ng/g, ww) and WHO PCB TEQs (2.85 pg/g,ww); their TEQ values are in the higher range of those reported in farmed salmon from around the world. Removal of skin from salmon fillets resulted in highly variable reductions of lipids and contaminants, and in some skin-off samples, contaminant levels were higher, suggesting that skin removal does not protect the consumer from health risks associated with consumption of farmed salmon.

Polychlorinated biphenyls and chlorinated pesticides in harbor seals (Phoca vitulina concolor) from the northwestern Atlantic coast.

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordane-related compounds (CHLs), mirex, hexachlorocyclohexane isomers (HCHs), dieldrin, and hexachlorobenzene (HCB) were determined in blubber of harbor seals (Phoca vitulina concolor) from the northwestern Atlantic coast. PCBs, DDTs, and CHLs were the major persistent organochlorines in harbor seal blubber, while mirex, HCHs, dieldrin, and HCB were minor contaminants. Highest concentrations were found in the adult males, followed by the pups, yearlings, adult females, and fetuses. DDT and PCB concentrations have declined from the high levels reported in the early 1970s, but no declines were observed in our samples over the ten-year period 1991-2001. DDT/PCB ratios were indicative of a more rapid decline of DDTs than PCBs, while ratios of p,p'-DDE/DDT were indicative of a metabolic "weathering" of DDT. The population appears to be susceptible to disease outbreaks, as evidenced by a recurrence of viral epizootics since the late 1970s. The PCB burdens in these seals are similar to levels reported in seals from polluted regions of Europe and Asia, and exceed the estimated threshold levels for adverse reproductive and immune system effects in the species.