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Blubber taken from ringed seals (Pusa hispida) during a subsistence hunt at Ulukhaktok, NT (formerly Holman, NWT) at intervals between 2002 and 2015 was analysed for polybrominated diphenyl ether (PBDE) congeners. Results from these analyses were combined with others previously published to yield a data set of 18 tri- to hepta-substituted PBDE congeners in 102 animals sampled over a span of 19 year (females) and 34 year (males). In females, mean total PBDE concentrations increased between 1996 and 2015 by approximately 50%, from 1940 to 2780 pg/g wet wt., although not significantly so (p > 0.05) by one-way ANOVA. In males, concentrations ranged from 376 to 6470 pg/g wet wt. between 1981 and 2015 (p < 0.05). In males, the most rapid increase in PBDE concentrations occurred before 2000, but between 2002 and 2015 mean total PBDE concentrations increased by a further 50%. ANCOVA showed PBDE concentrations in females to be correlated (p < 0.05) with sampling year but not with age or condition (as measured by blubber thickness); in males, PBDE concentrations were strongly correlated (p < 0.01) with year, age and condition. The relative proportions of tetra-bromo- congeners declined weakly in both sexes over the sampling period, with a compensatory increase in penta-bromo-congener distribution. Overall, the results show no evidence yet of a decline in PBDE concentrations in western Arctic ringed seals in response to voluntary and regulated restrictions on PBDE use in the early 2000s.

Commonly, analytical methods measuring brominated flame retardants (BFRs) of different chemical polarities in human serum are labor consuming and tedious. Our study used acidified diatomaceous earth as solid-phase extraction (SPE) adsorbent and defatting material to simultaneously determine the most abundant BFRs and their metabolites with different polarities in human serum samples. The analytes include three types of commercial BFRs, tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) isomers, and polybrominated biphenyl ethers (PBDEs), and dominant hydroxylated BDE (OH-PBDE) and methoxylated BDE (MeO-PBDE) metabolites of PBDEs. The sample eluents were sequentially analyzed for PBDEs and MeO-BDEs on online gel permeation chromatography/gas chromatography-electron capture-negative ionization mass spectrometry (online GPC GC-ECNI-MS) and for TBBPA, HBCD, and OH-BDEs on liquid chromatography-tandem mass spectrometry (LC-MS/MS). Method recoveries were 67-134% with a relative standard deviation (RSD) of less than 20%. Method detection limits (MDLs) were 0.30-4.20 pg/mL fresh weight (f.w.) for all analytes, except for BDE-209 of 16 pg/mL f.w. The methodology was also applied in a pilot study, which analyzed ten real samples from healthy donors in China, and the majority of target analytes were detected with a detection rate of more than 80%. To our knowledge, it is the first time for us in effectively determining BFRs of most types in one aliquot of human serum samples. This new analytical method is more specific, sensitive, accurate, and time saving for routine biomonitoring of these BFRs and for integrated assessment of health risk of BFR exposure.

Shellfish and sediment invertebrates have been widely used to assess pollution trends over space and time in coastal environments around the world. However, few studies have compared the bioaccumulation potential of different test species over a range of sediment-contaminant concentrations and profiles. The bioavailability of sediment-related contaminants was evaluated using sediments collected from sites (n = 12) throughout the Salish Sea, British Columbia, Canada. Two benthic marine invertebrates-the Baltic clam Macoma balthica and the polychaete worm Neanthes arenaceodentata-were exposed for 28 days in a controlled environment to these field-collected coastal sediments. The congener-specific uptake of legacy polychlorinated biphenyls (PCBs) and emergent polybrominated diphenyl ethers (PBDEs) was determined using high-resolution gas chromatography/mass spectrometry in sediments and in invertebrates after the experimental exposure. The polychaete Neanthes accumulated lower concentrations of PCBs but higher concentrations of PBDEs. The present study indicates that differences in bioaccumulation between these two invertebrates shape the accumulation of PCB and PBDE congeners, reflect differences in feeding strategies, and reveal the physicochemical properties of the contaminants and sediment properties. Because biota-sediment accumulation factor values are often calculated for environmental monitoring or site-specific impact assessments, our results provide insight into potentially confounding factors and the need for caution when selecting indicator species for coastal marine pollution.

We modeled temporal trends in polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and dichlorodiphenyltrichloroethane and its metabolites (DDTs) in two indicator fish species representing benthic and pelagic habitats in Puget Sound, Washington, USA. English sole (Parophrys vetulus, benthic) index sites and larger-scale Pacific herring (Clupea pallasii, pelagic) foraging areas represented a wide range of possible contamination conditions, with sampling locations situated adjacent to watersheds exhibiting high, medium and low development. Consistency in analytical data throughout the study was maintained by either calculating method-bias-correction factors on paired samples as methods evolved or by analyzing older archived samples by current methods. PCBs declined moderately in two herring stocks from a low-development basin (2.3 and 4.0% annual rate of decline) and showed no change in the highly developed and moderately developed basins during a 16- to 21-year period. PCBs increased in English sole from four of ten sites (2.9-7.1%), and the remaining six exhibited no significant change. PBDEs and DDTs declined significantly in all herring stocks (4.2-8.1%), although analytical challenges warrant caution in interpreting DDT results. PBDEs declined in English sole from two high-development and one low-development site (3.7-7.2%) and remained unchanged in the remaining seven. DDTs increased in English sole from one high-development site (Tacoma City Waterway) and declined in two high-development and one low development site. As with herring, analytical challenges warrant caution in interpreting the English sole DDT results. It is likely that source controls and mitigation efforts have contributed to the declines in PBDEs and DDTs overall, whereas PCBs appear to have persisted, especially in the pelagic food web, despite bans in PCB production and use.

B-cell lymphoma, a common morphologic variant of non-Hodgkin lymphoma, has been associated with persistent pollutants in humans, but this association is not well-characterized in top-level predators sharing marine resources with humans. We characterized and compared blubber contaminants and hormones of a pregnant harbor porpoise (Phocoena phocoena) with B-cell lymphoma, with those in two presumed healthy fishery by-caught porpoises with no lymphoma: a pregnant adult and female juvenile. Common historic use compounds, including polychlorinated biphenyls, polybrominated diphenyl ethers, and pesticides, were evaluated in blubber samples from three porpoises. In addition, blubber cortisol and progesterone levels (ng/g) were determined in all three animals. Total pollutant concentrations were highest in the juvenile porpoise, followed by the lymphoma porpoise and the nonlymphoma adult. Blubber cortisol concentrations were 191% greater in the pregnant with lymphoma porpoise compared with the pregnant no lymphoma porpoise, and 89% greater in the juvenile female compared with the pregnant no lymphoma porpoise. Although both adults were pregnant, progesterone levels were substantially greater (90%) in the healthy compared with the lymphoma adult. Health monitoring of top-level marine predators, such as porpoise, provides a sentinel measure of contaminants that serve as indicators of potential environmental exposure to humans.

For many years, it has been hypothesized that Neotropical migrants breeding in the United States and Canada accumulate organochlorine pesticides (OCPs) while on their wintering grounds in Latin America. We investigated the seasonal accumulation of persistent organic pollutant (POPs) in migrant and resident passerines in Texas, Yucatán, and Costa Rica collected during the fall, winter, and spring from 2011 to 2013. A total of 153 birds were collected, and all contained detectable levels of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and OCPs with dichlorodiphenyldichloroethylene (DDE) being the most predominant pesticide. OCPs and PCBs were the predominant contaminants, accounting for ≥80 % of the total POPs burden, whereas PBDEs accounted for ≤16 %. Only spring migrants from Texas had significantly greater DDE concentrations (64.6 ng/g dry weight [dw]) than migrants collected in Costa Rica (23.2 ng/g dw). Resident birds in Texas had significantly greater levels of DDE (121 ng/g dw) and ΣPBDEs (34.8 ng/g dw) compared with residents in Yucatán and Costa Rica. For ΣPCBs, resident birds from Costa Rica had significantly lower concentrations (9.60 ng/g dw) compared with their migrant counterparts (43.7 ng/g dw) and residents from Texas (48.3 ng/g dw) and the Yucatán (32.1 ng/g dw). Migrant and resident passerines had similar congener profiles for PCBs and PBDEs suggesting similar exposure and retention of these contaminants. No significant accumulation of DDE was observed in migrants while on their wintering grounds. Relatively high concentrations of PBDEs in resident birds from Costa Rica warrant future studies of PBDE contamination in Latin America.

During native subsistence hunts from 1987 to 2007, blubber and liver samples from 50 subadult male northern fur seals (Callorhinus ursinus) were collected on St. Paul Island, Alaska. Samples were analyzed for legacy persistent organic pollutants (POPs), recently phased-out/current-use POPs, and vitamins. The legacy POPs measured from blubber samples included polychlorinated biphenyl congeners, DDT (and its metabolites), chlorobenzenes, chlordanes, and mirex. Recently phased-out/current-use POPs included in the blubber analysis were the flame retardants, polybrominated diphenyl ethers, and hexabromocyclododecanes. The chemical surfactants, perfluorinated alkyl acids, and vitamins A and E were assessed in the liver samples. Overall, concentrations of legacy POPs are similar to levels seen in seal samples from other areas of the North Pacific Ocean and the Bering Sea. Statistically significant correlations were seen between compounds with similar functions (pesticides, flame retardants, vitamins). With sample collection spanning two decades, the temporal trends in the concentrations of POPs and vitamins were assessed. For these animals, the concentrations of the legacy POPs tend to decrease or stay the same with sampling year; however, the concentrations of the current-use POPs increased with sampling year. Vitamin concentrations tended to stay the same across the sampling years. With the population of northern fur seals from St. Paul Island on the decline, a detailed assessment of exposure to contaminants and the correlations with vitamins fills a critical gap for identifying potential population risk factors that might be associated with health effects.

Resident killer whale populations in the NE Pacific Ocean are at risk due to the accumulation of pollutants, including polybrominated diphenyl ethers (PBDEs). To assess the impact of PBDEs in water and sediments in killer whale critical habitat, we developed a food web bioaccumulation model. The model was designed to estimate PBDE concentrations in killer whales based on PBDE concentrations in sediments and the water column throughout a lifetime of exposure. Calculated and observed PBDE concentrations exceeded the only toxicity reference value available for PBDEs in marine mammals (1500 μg/kg lipid) in southern resident killer whales but not in northern resident killer whales. Temporal trends (1993-2006) for PBDEs observed in southern resident killer whales showed a doubling time of ≈5 years. If current sediment quality guidelines available in Canada for polychlorinated biphenyls are applied to PBDEs, it can be expected that PBDE concentrations in killer whales will exceed available toxicity reference values by a large margin. Model calculations suggest that a PBDE concentration in sediments of approximately 1.0 μg/kg dw produces PBDE concentrations in resident killer whales that are below the current toxicity reference value for 95 % of the population, with this value serving as a precautionary benchmark for a management-based approach to reducing PBDE health risks to killer whales. The food web bioaccumulation model may be a useful risk management tool in support of regulatory protection for killer whales.

We analyzed bat carcasses (Myotis lucifugus, M. sodalis, M. septentrionalis, and Eptesicus fuscus) from the northeastern United States for contaminants of emerging concern (CECs) such as polybrominated diphenyl ethers (PBDEs), and pharmaceuticals and personal care products. The CECs detected most frequently in samples were PBDEs (100 %), salicylic acid (81 %), thiabendazole (50 %), and caffeine (23 %). Other compounds detected in at least 15 % of bat samples were digoxigenin, ibuprofen, warfarin, penicillin V, testosterone, and N,N-diethyl-meta-toluamide (DEET). The CECs present at the highest geometric mean wet weight concentrations in bat carcasses were bisphenol A (397 ng/g), ΣPDBE congeners 28, 47, 99, 100, 153, and 154 (83.5 ng/g), triclosan (71.3 n/g), caffeine (68.3 ng/g), salicylic acid (66.4 ng/g), warfarin (57.6 ng/g), sulfathiazole (55.8 ng/g), tris(1-chloro-2-propyl) phosphate (53.8 ng/g), and DEET (37.2 ng/g). Bats frequently forage in aquatic and terrestrial habitats that may be subjected to discharges from wastewater-treatment plants, agricultural operations, and other point and nonpoint sources of contaminants. This study shows that some CECs are accumulating in the tissue of bats. We propose that CECs detected in bats have the potential to affect a number of physiological systems in bats including hibernation, immune function, and response to white-nose syndrome, a fungal disease causing population-level impacts to bats.

Halogenated organic pollutants (HOPs)-including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs), polybromobiphenyls (PBBs), dechlorane plus (DP), tetrabromobisphenol A (TBBPA), and hexabromocyclododecanes (HBCDs) as well as PCB metabolites (methylsulfone [MeSO2-]) and hydroxylated (OH-) PCBs and OH-PBDEs-were determined in the serum of mud carp and northern snakehead from an electronic-waste (e-waste) site in South China. The average concentrations (mean ± SD) of ΣPCBs, ΣPBDEs, ΣOCPs, ΣPBBs, ΣTBBPA, ΣHBCDs, and ΣDP were 1410 ± 324, 70 ± 20, 3.0 ± 0.4, 2.8 ± 0.8, 1.6 ± 0.4, 1.0 ± 0.2, and 0.3 ± 0.03 ng/g wet weight (ww) in mud carp and 6430 ± 781, 468 ± 49, 22.4 ± 1.1, 7.0 ± 0.6, 2.9 ± 2.3, 5.5 ± 1.1, and 4.6 ± 0.6 ng/g ww in northern snakehead, respectively. MeSO2-PCBs, OH-PCBs, and OH-PBDEs were detected at a total concentration of 0.44 ± 0.03 and 9.7 ± 0.3 ng/g ww in mud carp and northern snakehead, respectively. The congener profiles of PCBs, PBDEs, OH/MeSO2-PCBs, and OH-PBDEs were found to be significantly different between the two fish species, possibly as a result of species-specific bioaccumulation and/or metabolism of the HOPs. Chirality of ten PCB congeners and α-HBCD, as well as the f anti values of DP in the serum samples, supported the species-specific biotransformation of HOPs. Furthermore, the presence of covaried and counter-varied enantiomeric fractions of PCBs between the two fish species indicated species- and congener-specific enantiomer enrichment of PCBs.

As part of a broader study of budgets, transport, and bioaccumulation of persistent organic contaminants in the Strait of Georgia, Canada, matching samples of sediment and bulk benthos were collected near two marine sewage outfalls, two large urban harbours, and background areas. Samples were analyzed for polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) congeners. We present data for those congeners that fell within the top six rankings by concentration (23 PCBs and 10 PBDEs) within at least one of the environmental media measured in other studies (air, water, sediments, benthos, pelagic biota). Multifactor regression analyses incorporating sediment characteristics (total organic carbon, fines) predicted uptake (r (2) = 0.74 to 0.98, p < 0.04) over the range of congeners and habitats examined. PBDEs were taken up by biota more readily than PCBs, suggesting a large, potentially available biological reservoir of PBDEs in sediments. Dominant congeners in benthos comprised PBDEs 47, 99, 209, and 100 and PCBs 138/163, 153, 101, 118, and 110. PBDE uptake was anomalously high near one wastewater outfall, likely due to selective feeding on PBDE-enriched particulates from that source. Conversely, outfalls supply food and sediments with PCB concentrations similar to ambient sediments. However, organic enrichment of sediments near outfalls clearly enhanced PCB uptake by benthos, probably due to greatly increased biomass turnover near these sources. Data suggest there to be an initial reservoir of PCBs in newly settled juvenile benthos, which is much less evident for PBDEs. This is likely a consequence of the ecosystem-wide distribution of legacy PCBs but not the more current-use PBDEs. Congener-uptake patterns were dependent on source and input dynamics, feeding methods, and contaminant metabolism or debromination, particularly of deca-BDE.

Endocrine disruptors (EDs) from three chemical classes-polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates-were investigated in the Seine River and one tributary, the Orge River, upstream and downstream of urban areas. The impact of urban areas was characterized by a concentration increase of all compounds in the Seine River and for phthalates and PBDEs in the Orge River. In the Seine River, from upstream (Marnay) to downstream (Triel) of urban areas, water concentration increases were greater for diethylhexyl phthalate (DEHP) (6 times, p < 0.05) and ∑tri-hexa BDE (5 times [p < 0.05]) than for ∑7PCBi (2.6 times). Simultaneously, sediments displayed a strong accumulation of contaminants downstream and compared with upstream values, their concentrations increased greatly: 202-fold for DEHP, 69-fold for BDE209, 25-fold for ∑tri-hexa-BDE, and 11-fold for ∑7PCBi. Variations of fish ED concentrations gave an indication of their habitat contamination increase observed downstream of densely urbanized areas of the Seine River, especially for PBDEs (∑tri-hexa-PBDEs = 14-fold increase ≤15.7 ± 6.9 ng g(-1) dry weight [dw; p < 0.001]) and for PCBs (∑7PCBi eightfold increase ≤211 ± 55 ng g(-1) dw [p < 0.01]). PCA results highlighted relationships between the different ED classes. A correlation (p < 0.05) was observed between PCB and PBDE fish concentrations, suggesting common sources and similar absorption mechanisms. For PCBs, which were poorly biodegraded, the bioaccumulation factor was strongly correlated (p < 0.001) to molecular hydrophobicity, whereas for PBDEs a negative correlation (p < 0.05) was observed related active debromination processes. This multichemical study investigates for the first time the occurrence of a wide range of EDs in roach, which was chosen as a sentinel species for this survey of surface water contamination.

A number of bioactive brominated secondary metabolites, including hydroxylated polybrominated diphenyl ethers, have been isolated from algae, sponges, and bacteria. In the present study, a screening method using liquid-chromatography tandem mass spectrometry was developed for the identification and selective determination of dihydroxy (diOH), hydroxy-methoxy (OH-MeO), and dimethoxy (diMeO) analogs of tetra- to hexa-BDEs in marine biota. In negative atmospheric pressure chemical ionization (APCI) mode, diOH and OH-MeO analogs provided intense [M-H](-) ions, whereas diMeO analogs provided characteristic [M-Br+O](-) and [M-CH(3)](-) ions. This enabled the diOH-, OH-MeO-, and diMeO-PBDEs to be distinguished using selected reaction monitoring transitions in the APCI source. Recoveries of 2'-OH-6-MeO-2,3',4,5'-tetra-BDE in spiked marine samples were 84 ± 5 %, with a limit of quantification at 9.1 ng mL(-1) (signal-to-noise ratio = 10). The developed method was used to analyze two sponge species collected from Palau, Micronesia; the concentration ratio of diOH-tetra-BDE:OH-MeO-tetra-BDE was 10:1 for the Lamellodysidea sp., whereas it was 1:30 for the Callyspongia sp.

Swallows from two locations in the Rio Grande/Rio Bravo Basin and one reference site located 500 km away were analyzed for organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Of the OC pesticides, only p,p'-DDE was observed at levels of concern (carcass geometric mean range 642 to 8511 ng/g wet weight [ww]). DDE residues in carcass were significantly greater at El Paso than at other locations. PCBs were relatively low compared with locations in the northeastern United States and the Great Lakes. Geometric mean PBDE concentrations ranged from 18 to 258 ng/g ww (280 to 3395 ng/g lipid weight). PBDE congeners 47 and 99 comprised approximately 60% of total PBDEs. Concentrations of DDE measured in swallows from El Paso in 2000 and 2005 are among the highest observed in the last 20 years along the United States-Mexico border. The results from this study indicated that swallows are still being exposed to high concentrations of DDE, which could have adverse effects on reproduction or on predators that feed on swallows.

The surf scoter (Melanitta perspicillata) is a little-studied species of North American sea duck. Estimates suggest it has experienced a precipitous decline in breeding numbers over the latter half of the past century. To investigate the potential role of contaminant uptake and toxicity in the population decline, this study undertook to measure blood chemistry, porphyrin concentrations, EROD, and organic contaminants in mature surf scoters wintering in the Strait of Georgia, BC, Canada. Hepatic organochlorine pesticide, polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran, polychlorinated biphenyl (PCB), polybrominated diphenyl ether, and nonylphenol concentrations were relatively low; for example, SigmaTEQs (toxic equivalents) for PCBs, dioxins, and furans combined ranged from 4.7 ng/kg wet weight in reference-site (Baynes Sound) birds to 11.4 ng/kg wet weight in birds from Vancouver Harbour. Nonetheless, elevated EROD activity indicated that birds in Howe Sound were responding to an Ah-receptor-mediated stressor, which was also affecting hematocrit values and possibly vitamin A status. In addition, a low proportion of lymphocytes in individuals across locations in early spring samples was associated with poor body condition. The apparent loss of fitness just prior to the onset of northerly migrations to breeding grounds is of particular concern. Compromised health of mature birds at this point in the season might impact negatively on the productivity and survival of some individuals, particularly those overwintering in Howe Sound.