The vomeronasal organ and incisive duct of harbor seals are modified to secrete acidic mucus into the nasal cavity.

Most terrestrial mammals have a vomeronasal system to detect specific chemicals. The peripheral organ of this system is a vomeronasal organ (VNO) opening to the incisive duct, and its primary integrative center is an accessory olfactory bulb (AOB). The VNO in seals is thought to be degenerated like whales and manatees, unlike otariids, because of the absence of the AOB. However, olfaction plays pivotal roles in seals, and thus we conducted a detailed morphological evaluation of the vomeronasal system of three harbor seals (Phoca vitulina). The VNO lumen was not found, and the incisive duct did not open into the oral cavity but was recognized as a fossa on the anteroventral side of the nasal cavity. This fossa is rich in mucous glands that secrete acidic mucopolysaccharides, which might originate from the vomeronasal glands. The olfactory bulb consisted only of a main olfactory bulb that received projections from the olfactory mucosa, but an AOB region was not evident. These findings clarified that harbor seals do not have a VNO to detect some chemicals, but the corresponding region is a specialized secretory organ.

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 PBDEs have since been replaced by alternative legacy compounds or newly developed chemicals.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.

Integrated proteomics and metabolomics reveal the variations in the physiological state of spotted seal (Phoca largha) pups following artificial rescue.

Spotted seals (Phoca largha) are a critically endangered pinniped in China. Artificial rescue of newborn pups is a conventional method to enhance their survival and maintain the population. However, little is known about the variations in the physiological state of spotted seal pups following artificial rescue. Here, an integrated proteomics and metabolomics study was performed on spotted seal pups by using whole blood samples to characterize the molecular response to artificial rescue. The proteome was characterized as having 1165 proteins that were predominantly associated with the metabolic pathways, and the complement and coagulation cascades. Remarkable variation was found in spotted seal pup blood following artificial rescue, whereby the levels of 193 proteins and 32 metabolites significantly varied in some metabolic pathways, including glycosylphosphatidylinositol-anchor biosynthesis, focal adhesion, cardiac muscle contraction, and fatty acid beta-oxidation. After rescue, spotted seal pups had a higher risk to mild hemolytic disorder due to the energy metabolism in the red blood cells was possibly suppressed. Moreover, spotted seal pups after rescue could have stronger anaerobic exercise abilities, while their capacity for long-term high-intensity exercise was weaker.

Proteomics reveals the preliminary physiological states of the spotted seal (Phoca largha) pups.

Spotted seal (Phoca largha) is a critically endangered pinniped in China and South Korea. The conventional method to protect and maintain the P. largha population is to keep them captive in artificially controlled environments. However, little is known about the physiological differences between wild and captive P. largha. To generate a preliminary protein expression profile for P. largha, whole blood from wild and captive pups were subjected to a label-free comparative proteomic analysis. According to the results, 972 proteins were identified and predicted to perform functions related to various metabolic, immune, and cellular processes. Among the identified proteins, the expression level of 51 were significantly different between wild and captive P. large pups. These differentially expressed proteins were enriched in a wide range of cellular functions, including cytoskeleton, phagocytosis, proteolysis, the regulation of gene expression, and carbohydrate metabolism. The abundances of proteins involved in phagocytosis and ubiquitin-mediated proteolysis were significantly higher in the whole blood of wild P. largha pups than in captive individuals. In addition, heat shock protein 90-beta, were determined as the key protein associated with the differences in the wild and captive P. largha pups due to the most interactions of it with various differentially expressed proteins. Moreover, wild P. largha pups could be more nutritionally stressed and have more powerful immune capacities than captive pups. This study provides the first data on the protein composition of P. largha and provides useful information on the physiological characteristics for research in this species.

Response of metabolic hormones and blood metabolites to realimentation in rehabilitated harbor seal (Phoca vitulina) pups.

Mammals with increased requirements for adipose tissue stores, such as marine mammals, have altered nutrient allocation priorities compared to many terrestrial mammals and thus the physiological response to undernutrition (low nutritional status) and realimentation (refeeding) may differ. Key regulators of nutrient allocation and tissue specific growth include metabolic hormones of the somatotropic axis, growth hormone (GH) and insulin-like growth factor (IGF)-I, as well as satiety and adipose promoting ghrelin and the stress hormone cortisol. Longitudinal measurements of metabolic hormones, blood metabolites, and morphometrics were collected over a 10-week period in twelve (male n = 3, female n = 9) harbor seal pups (< 6 weeks of age). Blood metabolites were used to indicate metabolic response during realimentation while morphometrics estimated tissue specific growth priorities. Harbor seal pups undergoing refeeding after nutritional deprivation show a preference for protein sparing despite severe malnutrition. Both BUN and total protein were negatively associated with GH and positively associated with IGF-I and ghrelin highlighting the importance of these metabolic hormones in the regulation of protein metabolism. While the response of the somatotropic axis to realimentation was typical of the mammalian pattern, the surprising increase of ghrelin across the study period suggests the priority of adipose accretion in addition to a possible mechanism regulating compensatory growth of vital adipose stores in a species, which prioritizes adipose accretion for survival.

Trace Element Concentrations in Livers of Pacific Harbor Seals (Phoca vitulina richardii) from San Juan County, Washington, USA.

Approximately 5,000 Pacific harbor seals (Phoca vitulina richardii) reside year-round in San Juan County (SJC), Washington (US) in the center of the binational Salish Sea. We retrospectively analyzed total cadmium (Cd), copper (Cu), iron (Fe), mercury (Hg), magnesium (Mg), manganese (Mn), lead (Pb), selenium (Se), and zinc (Zn) in livers of dead stranded harbor seals (n=57) collected in SJC between 2009 and 2012 to identify age-related and regional patterns of trace element exposure. Consistent with prior studies of contaminants in pinnipeds, Hg, Cd, and Se concentrations increased with age, and Se:Hg molar ratios approached 1:1 in adult seals. Concentrations of Cd and Hg were below putative marine mammal toxicity thresholds. Mercury concentrations were comparable among Salish Sea populations. Although SJC is less urbanized with fewer industrial inputs than South Puget Sound (SPS), SJC nonpups had greater concentrations of Cd, Cu, and Zn, and pups had greater concentrations of Zn compared to SPS seals. We hypothesize these regional differences could be due to prey preference and availability or to natural geochemical processes. Reported concentrations inform future sampling protocols and can assist in tracking long-term temporal and spatial trends of trace elements in marine organisms.

Trends of persistent organic pollutants in ringed seals (Phoca hispida) from the Canadian Arctic.

Ringed seals (Phoca hispida) have been used as bioindicator species of environmental contamination in Canada since the 1970s. In the present study, seals were harvested during subsistence hunts in four regions of the Canadian Arctic: Beaufort Sea, Arctic Archipelago, Hudson Bay, and coastal Labrador. An extensive suite of persistent organic pollutants (POPs) was determined in seal blubber collected for multiple years between 1972 and 2016. Results from this long-term study indicate geographical differences in the contaminant concentrations in seals and the significant general decrease of most POPs, including polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and related compounds, chlordanes (CHL), and hexachlorocyclohexanes (HCH) over time in ringed seals. The highest decrease rates (up to -9.1%/year for α-HCH) were found in seals from the Hudson Bay region where all chemicals investigated have significantly decreased since 1986. Significant increases in concentrations of hexachlorobenzene (HCB) in seals from Labrador and ß-HCH in Sachs Harbour, NT and Arctic Archipelago were observed. Site-specific and contaminant-specific associations between climate pattern (i.e., Arctic Oscillation, North Atlantic Oscillation, and Pacific/North American pattern) and mean ice-coverage (total, first-year ice, and old-ice) were found at sites with the longest time trend data (i.e., Arviat, Sachs Harbour/Ulukhaktok and Resolute Bay). Overall, results suggest that North American and international regulations have led to the long-term reduction of most POPs in Canadian Arctic ringed seals by reducing emissions from primary sources. However, other sources of legacy compounds (e.g., environmental reservoirs) as well changes in food web composition and structure in relation to climate changes could also be influencing the very slow rates of decline, or stable levels, of contaminants found in seals at some sites. Further work is warranted to discern between co-variation of climate changes and contaminant concentrations and cause-and-effect relationships.

Organ-specific differences in mercury speciation and accumulation across ringed seal (Phoca hispida) life stages.

Methylmercury (MeHg) is a central nervous system toxicant and exposures can adversely affect the health of marine mammals. Mercuric selenide (HgSe) in marine mammal tissues is hypothesized to result from a protective detoxification mechanism, but toxicokinetic processes contributing to its formation are poorly understood. Here, new data is reported on speciated Hg concentrations in multiple organs of n = 56 ringed seals (Phoca hispida) from Labrador, Canada, and compare concentrations to previously published data from Greenland seals. A higher proportion of Hg is found to accumulate in the kidney of young-of-the-year (YOY) ringed seals compared to adults. A toxicokinetic model for Hg species is developed and evaluated to better understand factors affecting variability in Hg concentrations among organs and across life stages. Prior work postulated that HgSe formation only occurs in the liver of mature seals, but model results suggest HgSe formation occurs across all life stages. Higher proportions of HgSe in mature seal livers compared to YOY seals likely results from the slow accumulation and elimination of HgSe (total body half-life = 500 days) compared to other Hg species. HgSe formation in the liver reduces modeled blood concentrations of MeHg by only 6%. Thus, HgSe formation may not substantially reduce MeHg transport across the blood-brain barrier of ringed seals, leaving them susceptible to the neurotoxic effects of MeHg exposure.

Oil fouling in three subsistence-harvested ringed (Phoca hispida) and spotted seals (Phoca largha) from the Bering Strait region, Alaska: Polycyclic aromatic hydrocarbon bile and tissue levels and pathological findings.

Oil spills of unknown origin were detected in three oil-fouled, ice-associated seals from the Alaska Bering Strait region collected by Alaska Native subsistence hunters during fall 2012. Bile analyses of two oiled seals indicated exposure to fluorescent polycyclic aromatic hydrocarbon (PAH) metabolites but levels of some metabolites were similar to or lower than biliary levels in harvested unoiled ice seals. Oiled seals had elevated tissue PAH concentrations compared to tissue levels of PAHs determined in unoiled ice seals. However, regardless of oiling status, tissue PAH levels were relatively low (<50 ng/g, wet weight) likely due to rapid PAH metabolism and elimination demonstrated previously by vertebrates. Hepatic, pulmonary, and cardiac lesions were observed in oiled seals in conjunction with measurable PAHs in their tissue and bile. This is the first study to report tissue and bile PAH concentrations and pathologic findings of oiled ice seals from the U.S. Arctic.

Nuclear reprocessing-related radiocarbon (14C) uptake into UK marine mammals.

To evaluate the transfer of Sellafield-derived radiocarbon (14C) to top predators in the UK marine environment, 14C activities were examined in stranded marine mammals. All samples of harbour porpoise (Phocoena phocoena) obtained from the Irish Sea showed 14C enrichment above background. Mammal samples obtained from the West of Scotland, including harbour porpoise, grey seals (Halichoerus grypus) and harbour seals (Phoca vitulina) showed 14C enrichment but to a lesser extent. This study demonstrates, for the first time, enriched 14C is transferred through the marine food web to apex predators as a consequence of ongoing nuclear reprocessing activities at Sellafield. Total Sellafield 14C discharge activity 24months prior to stranding and, in particular, distance of animal stranding site from Sellafield are significant variables affecting individual 14C activity. 14C activities of West of Scotland harbour porpoises suggest they did not forage in the Irish Sea prior to stranding, indicating a high foraging fidelity.

Spatial and temporal trends of alternative flame retardants and polybrominated diphenyl ethers in ringed seals (Phoca hispida) across the Canadian Arctic.

Concentrations of alternative flame retardants and polybrominated diphenyl ethers (PBDEs) were analyzed in ringed seal (Phoca hispida) blubber collected across the Canadian Arctic during subsistence hunts between 1998 and 2013. More than 80% of sampled animals were females and juvenile males. The highest mean ΣPBDE concentrations (sum of 13 congeners) were found in seals from Nain (Nunatsiavut) as well as Inukjuaq and Arviat (Hudson Bay) and the lowest mean levels were found in seals from Lancaster Sound. BDE-47 and -99 were the predominant PBDE congeners quantified in ringed seals. The most frequently detected non-PBDE flame retardants were polybrominated biphenyl 101 (BB-101, 57% of samples analyzed for this chemical), hexabromocyclododecane (HBCDD; 38%), hexabromobenzene (HBB, 30%), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB, 23%). The relative trophic position of seals, estimated using stable isotopes, did not vary over time and did not influence flame retardant blubber concentrations. The relative carbon source increased over time at Arviat and Resolute Bay and weak relationships were observed with ΣPBDEs in blubber of seals. ΣPBDEs increased significantly from 1998 to 2008 in ringed seals from East Baffin and subsequently decreased in recent years. PBDE levels at other sites fluctuated slightly over time. HBCDD concentrations increased at several sites over the past decade. The presence of flame retardants in ringed seals suggests their persistence and their continuous inputs in the Canadian Arctic environment. Monitoring and research on the effects of these contaminants in seals are warranted given the importance of this species in Arctic marine food webs and for local communities.

Xenobiotic and Immune-Relevant Molecular Biomarkers in Harbor Seals as Proxies for Pollutant Burden and Effects.

Harbor seals are exposed to increasing pressure caused by anthropogenic activities in their marine environment. Persistent organic pollutants (POPs) and trace elements are hazardous contaminants that accumulate in tissues of harbor seals. POPs and trace elements can negatively affect the immune-system and have been reported, e.g., to increase susceptibility to viral infections in seals. Biomarkers of the xenobiotic metabolism, cytokines, and heat-shock protein as cell mediators of the immune-system were established to evaluate the impact of environmental stressors on harbor seals. Harbor seals (n = 54) were captured on sandbanks in the North Sea during 2009-2012. Health assessments, including hematology, were performed, and RNAlater blood samples were taken and analyzed using quantitative polymerase chain reaction. Normalized transcript copy numbers were correlated to hematology and POP concentration in blood and trace metals in blood and fur. A significant correlation between xenobiotic markers and contaminant burden was found. Significant interrelationships between markers and POP compounds, as well as with season, weight, and hematology values, indicate that biomarkers reflect pollutant exposure and effects. A significant relationship between cortisol levels and heat-shock protein expression was observed indicating stress experienced during restraint of the seals. Interleukin-10 transcription showed significant correlations with trace elements in fur pointing toward immune regulatory effects of metal exposure. The molecular markers prove to be an important noninvasive tool that reflects contaminant exposure and the impact of anthropogenic stressors in seal species. The connection between interleukin-2, xenobiotic markers, and pollutants may indicate immune suppression in animals exposed to contaminants with subsequent susceptibility to inflammatory disease.

Variation in bioaccumulation of persistent organic pollutants based on octanol-air partitioning: Influence of respiratory elimination in marine species.

Risk assessments of persistent organic pollutants (POPs) are often based on octanol-water (KOW) partitioning dynamics and may not adequately reflect bioaccumulation in air-breathing organisms. It has been suggested that compounds with low KOW and high octanol-air partitioning (KOA) coefficients have the potential to bioaccumulate in air-breathing organisms, including marine mammals. Here we evaluate differences in concentrations of POPs for two trophically matched Arctic species, spotted seal (Phoca largha) and sheefish (Stenodus leucichthys). We compared concentrations of 108 POPs in matched tissues (liver and muscle) across three ranges of KOW. We found a significant positive correlation between POP concentration and log KOA in spotted seal tissues for low log KOW compounds (log KOW <5.5, p<0.05). This provides further evidence for empirical models and observed bioaccumulation patterns in air-breathing organisms, and highlights the potential for bioaccumulation of these compounds in Arctic marine mammals.

Uridine Diphosphate-Glucuronosyltransferase (UGT) Xenobiotic Metabolizing Activity and Genetic Evolution in Pinniped Species.

There are various interspecies differences in xenobiotic-metabolizing enzymes. It is known that cats show slow glucuronidation of drugs such as acetaminophen and strong side effects due to the UGT1A6 pseudogene. Recently, the UGT1A6 pseudogene was found in the Northern elephant seal and Otariidae was suggested to be UGT1A6-deficient. From the results of measurements of uridine diphosphate-glucuronosyltransferase (UGT) activity using liver microsomes, the Steller sea lion, Northern fur seal, and Caspian seal showed UGT activity toward 1-hydroxypyrene and acetaminophen as low as in cats, which was significantly lower than in rat and dog. Furthermore, UGT1A6 pseudogenes were found in Steller sea lion and Northern fur seal, and all Otariidae species were suggested to have the UGT1A6 pseudogene. The UGT1 family genes appear to have undergone birth-and-death evolution based on a phylogenetic and synteny analysis of the UGT1 family in mammals including Carnivora. UGT1A2-1A5 and UGT1A7-1A10 are paralogous genes to UGT1A1 and UGTA6, respectively, and their numbers were lower in cat, ferret and Pacific walrus than in human, rat, and dog. Felidae and Pinnipedia, which are less exposed to natural xenobiotics such as plant-derived toxins due to their carnivorous diet, have experienced fewer gene duplications of xenobiotic-metabolizing UGT genes, and even possess UGT1A6 pseudogenes. Artificial environmental pollutants and drugs conjugated by UGT are increasing dramatically, and their elimination to the environment can be of great consequence to cat and Pinnipedia species, whose low xenobiotic glucuronidation capacity makes them highly sensitive to these compounds.

Endocrine and immunological responses to adrenocorticotrophic hormone (ACTH) administration in juvenile harbor seals (Phoca vitulina) during winter and summer.

There is increasing interest in measuring endocrine and immune parameters in free-ranging seals and sea lions, but there is a lack of understanding in how an acute stress response, often associated with capture and handling, influences these parameters of interest. The main objective of this study was to assess the impact of a simulated stressor on both endocrine and immune parameters. During two seasons, exogenous adrenocorticotrophic hormone (ACTH) was administered to seven female juvenile harbor seals and the response of several hormones (cortisol, aldosterone, total and free thyroxine and total triiodothyronine) and immunological parameters (total and differential leukocyte counts and peripheral blood mononuclear cells (PBMC) proliferation) were assessed. Cortisol peaked at 165 min (winter 203.1±84.7 ng/ml; summer 205.3±65.7 ng/ml) and remained significantly elevated 240 min after ACTH infusion in both seasons. Aldosterone peaked at 90 min (winter 359.3±249.3 pg/ml; summer 294.1±83.7 pg/ml) and remained elevated 240 min after administration of ACTH in both seasons. An increase in circulating total white blood cells was driven primarily by the increase in neutrophils which occurred simultaneously with a decrease in lymphocytes leading to an overall increase in neutrophil to lymphocyte ratio. These findings demonstrate that a simulated stress response in juvenile harbor seals results in a predictable increase in both cortisol and aldosterone concentrations, and were associated with altered immunological parameters.

Detection and effects of harmful algal toxins in Scottish harbour seals and potential links to population decline.

Over the past 15 years or so, several Scottish harbour seal (Phoca vitulina) populations have declined in abundance and several factors have been considered as possible causes, including toxins from harmful algae. Here we explore whether a link could be established between two groups of toxins, domoic acid (DA) and saxitoxins (STXs), and the decline in the harbour seal populations in Scotland. We document the first evidence that harbour seals are exposed to both DA and STXs from consuming contaminated fish. Both groups of toxins were found in urine and faeces sampled from live captured (n = 162) and stranded animals (n = 23) and in faecal samples collected from seal haul-out sites (n = 214) between 2008 and 2013. The proportion of positive samples and the toxins levels measured in the excreta were significantly higher in areas where harbour seal abundance is in decline. There is also evidence that DA has immunomodulatory effects in harbour seals, including lymphocytopenia and monocytosis. Scottish harbour seals are exposed to DA and STXs through contaminated prey at potentially lethal levels and with this evidence we suggest that exposure to these toxins are likely to be important factors driving the harbour seal decline in some regions of Scotland.

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.

Simultaneous detection of multiple hydroxylated polychlorinated biphenyls from a complex tissue matrix using gas chromatography/isotope dilution mass spectrometry.

In this study, we developed a comprehensive, highly sensitive, and robust method for determining 53 congeners of three to eight chlorinated OH-PCBs in liver and brain samples by using isotope dilution gas chromatography (GC) coupled with electron capture negative ionization mass spectrometry (ECNI-MS). These results were compared with those from GC coupled with electron ionization high-resolution mass spectrometry (EI-HRMS). Clean-up procedures for analysis of OH-PCBs homologs in liver and brain samples involve a pretreatment step consisting of acetonitrile partition and 5% hydrated silica-gel chromatography before derivatization. Recovery rates of tri- and tetra-chlorinated OH-PCBs in the acetonitrile partition method followed by the 5% hydrated silica-gel column (82% and 91%) were higher than conventional sulfuric acid treatment (2.0% and 3.5%). The method detection limits of OH-PCBs for each matrix obtained by GC/ECNI-MS and GC/EI-HRMS were 0.58-2.6 pg g(-1) and 0.36-1.6 pg g(-1) wet wt, respectively. Recovery rates of OH-PCB congeners in spike tests using sample matrices (10 and 50 pg) were 64.7-117% (CV: 4.7-14%) and 70.4-120% (CV: 2.3-12%), respectively. This analytical method may enable the simultaneous detection of various OH-PCBs from complex tissue matrices. Furthermore, this method allows more comprehensive assessment of the biological effects of OH-PCB exposure on critical organs.

Temporal trends in "legacy" organochlorine contaminants in blubber of ringed seals (Phoca hispida) from Ulukhaktok, NT, Canada between 1972 and 2010.

In blubber of ringed seals (Phoca hispida) from Ulukhaktok, NT, residues of DDT, other organochlorine pesticides, and PCBs declined between 1972 and 2010. The rate of decline varied: concentrations of the DDT-group began to fall after 1981, whereas those of PCBs fell rapidly between 1972 and 1981, and then slowed. Concentrations of cis- and trans-chlordane and of HCB in both sexes, and of cis-nonachlor in males, declined slowly between 1978 and 2010; those of other organochlorine pesticides remained steady. Exponential half-lives of p,p'-DDT and p,p'-DDE in female seals are about 9 and 36 y (corresponding to initial declines of 7.8% and 1.9% per year, respectively) and those of PCB congeners from about 20 to 60 y (declines of 3.2% to <1.5% per year); the more refractory residues may be detectable for centuries to come. Exploratory PCA of PCB congener distribution identified temporal changes apparently not related to molecular structure.