Occurrence and tissue-specific partitioning of alternative brominated flame retardants in northwest Atlantic harbor seal pups (Phoca vitulina vitulina).

Brominated flame retardants such as polybrominated diphenyl ethers (PBDEs) have been used for decades until evidence of negative health effects led to bans in many countries. PBDEs have since been replaced by alternative legacy compounds or newly developed chemicals. In this study, eight alternative brominated flame retardants were analyzed in blubber and liver of harbor seal pups (≤6 months) from the Northwest Atlantic collected during 2001-2010 to elucidate concentrations, patterns, contamination trends, potential maternal transfer, and tissue partitioning. All compounds were detected in liver and blubber tissues with hexabromocyclododecane (HBCD) isomers and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) predominating. Overall, α-HBCD was the dominant HBCD isomer in both tissues although the concentrations of γ-HBCD exceeded those of α-HBCD in seven pups, indicating their mothers may have had alternative dietary patterns or recent exposure to the commercial mixture. Although it was detected in less than half of the samples, to our knowledge, this is the first study to report tetrabromobisphenol A (TBBPA) concentrations in multiple tissues of a top marine predator. For the brominated components of Firemaster® flame retardants, TBB concentrations exceeded bis-(2-ethylhexyl)-tetrabromophthalate (TBPH). This pattern may result from recent exposure to commercial mixtures in which TBB exceeds TBPH 4:1 or from differences in perinatal or lactational transfer efficiency of the two compounds. Between the two tissues, lipid-normalized ß-HBCD, γ-HBCD, TBB and decabromodiphenyl ethane (DBDPE) concentrations were significantly higher in liver than blubber. This indicates that the bioaccumulation of these chemicals is not simply related to lipid dynamics but may be linked to blood proteins. This study demonstrates that harbor seal pups from this region are contaminated with alternative flame retardants passed to them via placental or lactational transfer. Given the evidence for negative health effects of these chemicals, this contamination adds additional pressure on the first year survival of these young, developing animals.

Alternative and legacy flame retardants in marine mammals from three northern ocean regions.

Flame retardants are globally distributed contaminants that have been linked to negative health effects in humans and wildlife. As top predators, marine mammals bioaccumulate flame retardants and other contaminants in their tissues which is one of many human-imposed factors threatening population health. While some flame retardants, such as the polybrominated diphenyl ethers (PBDE), have been banned because of known toxicity and environmental persistence, limited data exist on the presence and distribution of current-use alternative flame retardants in marine mammals from many industrialized and remote regions of the world. Therefore, this study measured 44 legacy and alternative flame retardants in nine marine mammal species from three ocean regions: the Northwest Atlantic, the Arctic, and the Baltic allowing for regional, species, age, body condition, temporal, and tissue comparisons to help understand global patterns. PBDE concentrations were 100-1000 times higher than the alternative brominated flame retardants (altBFRs) and Dechloranes. 2,2',4,5,5'-pentabromobiphenyl (BB-101) and hexabromobenzene (HBBZ) were the predominant altBFRs, while Dechlorane-602 was the predominant Dechlorane. This manuscript also reports only the second detection of hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO) in marine mammals. The NW Atlantic had the highest PBDE concentrations followed by the Baltic and Arctic which reflects greater historical use of PBDEs in North America compared to Europe and greater industrialization of North America and Baltic countries compared to the Arctic. Regional patterns for other compounds were more complicated, and there were significant interactions among species, regions, body condition and age class. Lipid-normalized PBDE concentrations in harbor seal liver and blubber were similar, but HBBZ and many Dechloranes had higher concentrations in liver, indicating factors other than lipid dynamics affect the distribution of these compounds. The health implications of contamination by this mixture of compounds are of concern and require further research.

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.

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.

Methoxylated PBDEs (MeO-PBDEs), hydroxylated PBDEs (HO-PBDEs) and hydroxylated PCBs (HO-PCBs) in the liver of harbor seals from the northwest Atlantic.

Metabolites of PCBs and PBDEs are shown to influence the thyroid hormone homeostasis and therefore, could have an influence on the growth of newborn or young animals. We have investigated the occurrence of hydroxylated PCBs (HO-PCBs), hydroxylated PBDEs (HO-PBDEs), and methoxylated PBDEs (MeO-PBDEs) in the liver (48 pups; 6 adults) and blubber (4 pups; 1 adult) of harbor seals (Phoca vitulina concolor) from the northwest Atlantic. The sum of HO-PCBs in the liver ranged from 90 to 22,450 pg/g wet weight (ww) for pups and from 410 to 5290 pg/g ww for adults. Congener 4-HO-CB 107 was predominant in almost all samples regardless of age or gender, except in one adult male. Sum HO-PCB concentrations were highly correlated with the sum of precursor PCBs in the liver of harbor seals (r(2) = 0.79; p<0.0001). Concentrations of sum HO-PBDEs in the liver ranged from 70 to 1850 pg/g ww for pups and from 90 to 230 pg/g ww for adults. HO-PBDEs were also correlated with PBDEs (r(2) = 0.58; p<0.0001). Sum MeO-PBDE concentrations in the liver ranged from 20 to 1460 pg/g ww in pups and from 10 to 270 pg/g ww in adults. HO-PCBs and HO-PBDEs were not detected in the blubber. Levels of MeO-PBDEs in the blubber ranged from 1500 to 4400 pg/g ww. In all blubber samples, 6-MeO-BDE 47 was the predominant MeO-PBDE congener, followed by 2'-MeO-BDE 68 and 5-MeO-BDE 47, respectively. The presence of HO-metabolites in pup liver suggests that young harbor seals may have some, yet limited, metabolic capacity for PCBs and PBDEs, which can lead to an excessive accumulation of these chemicals in the body. Moreover, the presence of HO-PCB and HO-PBDE metabolites may pose an additional stress for young harbor seals due to their influence on the thyroid hormone system and could have consequences for the entire population.

Polychlorinated biphenyls still pose significant health risks to northwest Atlantic harbor seals.

Polychlorinated biphenyls (PCBs) have been detected at relatively high concentrations in harbor seals, apex predators in the northwest Atlantic. As part of an ongoing assessment of the effects of PCBs on population health, we analyzed tri- to deca-PCBs in the liver of 56 harbor seals (6 adult males, 50 pups) and in 11 blubber samples (4 adult males, 7 pups) and examined tissue-specific accumulation patterns, biomagnification potential, and toxic implications of current PCB concentrations. Hepatic ∑30PCB concentrations (overall mean±standard deviation: 76,860±111,800 ng/g lipid weight, lw) were higher than blubber concentrations (48,180±69,420 ng/g lw). Regional trends were suggestive of fresh PCB inputs from the industrialized, densely populated southern coast of New England versus the rural north. The lack of temporal trends confirmed that tissue concentrations of PCBs have plateaued since the early 1990s. Tissue distribution of PCBs varied significantly by age and, surprisingly by gender among the pups. Principal Component Analysis (PCA) revealed that lighter PCBs are selectively transferred from mother to pup blubber in relation to lipid solubility (log Kow), but heavier PCBs may be efficiently transferred during late lactation from mother to pup liver. Biomagnification factors (BMFs) for ∑6PCBs from prey fish to adult male seals ranged from 90 to 547 in the liver and 88 to 532 in the blubber, and suggested that molecular structure and metabolic capacity were more important influences than log Kow on the retention of PCBs. Blubber concentrations of ∑30PCBs in 87% of the pups were an order of magnitude higher than recent toxic reference values (TRVs) calculated for ∑154PCBs in nursing harbor seals, suggesting that the pups are at risk for PCB-mediated toxicity at a vulnerable stage of development. Given the recurring pattern of epizootics in these seals, the health of the population is of concern.

Persistent organic pollutants including polychlorinated and polybrominated dibenzo-p-dioxins and dibenzofurans in firefighters from Northern California.

Polychlorinated and polybrominated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs and PBDD/Fs) were measured in serum of twelve firefighters sampled after a fire event in San Francisco, California, along with polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), p,p'-DDE, hexachlorobenzene (HCB), perfluorinated chemicals (PFCs), bisphenol-A (BPA) and tetrabromobisphenol-A (TBBPA). TEQPCDD/F concentrations were relatively low (mean 5pgg(-1) (lipid weight), lw, range 1-11pgg(-1)lw), but concentrations of 1,2,3,4,6,7,8-HpCDD, a congener indicative of exposure during firefighting, were elevated. Tentative WHO2005-TEQs calculated for PBDD/Fs in our samples (mean 104pgg(-1)lw, range 0.2-734pgg(-1)lw) suggested that PBDD/Fs may contribute substantially to dioxin-like toxicity in individual firefighters. PBDE concentrations were elevated in firefighter serum (mean 135ngg(-1)lw, range 48-442ngg(-1)lw). PBDE-209, PBDE-47 and PBDE-153 were prevalent congeners; PBDE-209 contributed >50% of the total PBDE concentration in four individuals, implying continuous occupational exposure to deca-BDE. Perfluorooctanesulfonate (PFOS) was the dominant PFC in serum (mean 12ngml(-1) (wet weight), ww, range 3ngml(-1)ww to 59ngml(-1)ww), followed by perfluorooctanoic acid (PFOA) (mean 7ngml(-1)ww, range 2ngml(-1)ww to 12ngml(-1)ww). Concentrations of perfluorononanoic acid (PFNA) (mean 2ngml(-1)ww, range 1-4ngml(-1)ww) were higher than those reported in the high-smoke exposure group of World Trade Center fire responders, suggesting that the California firefighters were exposed to PFNA in smoke during firefighting. Given their elevated rates of cancers, these results illustrate the importance of monitoring halogenated contaminants including PBDD/Fs in firefighters.

Tissue-specific accumulation of polybrominated diphenyl ethers (PBDEs) including Deca-BDE and hexabromocyclododecanes (HBCDs) in harbor seals from the northwest Atlantic.

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) are widely used flame retardants that enter coastal waters from multiple sources and biomagnify in marine food webs. PBDEs have been detected at relatively high concentrations in harbor seals, apex predators in the northwest Atlantic. Whereas tri- to hexa-BDEs readily biomagnified from prey fishes to seal blubber, Deca-BDE (BDE-209) did not biomagnify in blubber. To explore tissue-specific differences in the accumulation/biomagnification of BFRs, we analyzed tri- to Deca-BDES in liver of 56 harbor seals (6 adult males, 50 pups), and compared hepatic concentrations and biomagnification potential with those in blubber. HBCDs were analyzed in seal liver and blubber to enable similar comparisons. Hepatic ΣPBDE (tri- to Octa-BDE) concentrations (range 35-19,547ng/glipid weight, lw) were similar to blubber concentrations, while α-HBCD levels in seal liver (range 2-279ng/glw) were significantly higher than levels in blubber. Tissue distribution of PBDEs and α-HBCD varied significantly by age and, surprisingly, by gender among the pups. Biomagnification of α-HBCD from fish to seal liver and blubber was negligible to low, implying that harbor seals can metabolize this persistent isomer. Similar to the patterns in blubber, tri- through hexa-BDEs were highly biomagnified from fish to seal liver. In contrast, BDE-209 concentrations in liver were up to five times higher than those in blubber, which is consistent with observations that BDE-209 migrates to perfused tissues such as the liver in biota. Although detection frequency was low, BDE-209 levels in seal liver were up to ten times higher than those in their prey fish, suggesting that the accumulation/biomagnification of Deca-BDE in marine food webs is tissue-specific. As BDE-209 is the dominant PBDE found in marine sediments, its biomagnification in marine ecosystems is of concern.

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.

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.