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The present study determined recent accumulation levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), polychlorinated diphenyl ethers (PCDEs), methoxylated-PBDEs (MeO-PBDEs) and 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1) in the blubber of melon-headed whales (Peponocephala electra) stranded along the Japanese coastal waters in 2015 and examined temporal trends of these organohalogen compound (OHC) levels by analyzing blubber samples of this species archived in the environmental specimen bank which were collected in 1982, 2001, 2002, 2006, 2010 and 2011. The median concentrations in melon-headed whales stranded recently were in the order of DDTs ≈ PCBs > HBCDDs > Q1 > CHLs > MeO-PBDEs > PBDEs > HCB > HCHs > PCDEs, indicating that considerable amounts of HBCDDs, in addition to DDTs and PCBs, have been transported to tropical and subtropical waters of the open ocean and pelagic whale species might be exposed to relatively high levels of these OHCs. Temporal trend analyses of OHC levels in the blubber of melon-headed whales revealed significant decrease for anthropogenic OCs such as DDTs, PCBs, HCB, HCHs and PCDEs, and significant increase for CHLs, PBDEs, HBCDDs, MeO-PBDEs and Q1 since 1982. Besides, the analyses from 2001 to 2015 showed no decreasing trends (unchanged) for some PCB congeners, p,p’-DDE, cis- and trans-nonachlors, Q1, BDE-47, -100 and −154, and significantly increasing trends for α-HBCDD and 6MeO-BDE47, suggesting their chronic exposure for this pelagic whale species.

Despite decades-long bans on the production and use of certain chemicals, many halogenated organic compounds (HOCs) are persistent and can bioaccumulate in the marine environment with the potential to cause physiological harm to marine fauna. Highly lipid-rich tissue (e.g., marine mammal blubber) functions as a reservoir for HOCs, and selecting ideal indicator species is a priority for retrospective and proactive screening efforts. We selected five marine mammal species as possible indicators for the Southern California Bight (SCB) and applied a non-targeted analytical method paired with an automated data reduction strategy to catalog a broad range of known, known but unexpected, and unknown compounds in their blubber. A total of 194 HOCs were detected across the study species (n = 25 individuals), 81% of which are not routinely monitored, including 30 halogenated natural products and 45 compounds of unknown structure and origin. The cetacean species (long-beaked common dolphin, short-beaked common dolphin, and Risso's dolphin) averaged 128 HOCs, whereas pinnipeds (California sea lion and Pacific harbor seal) averaged 47 HOCs. We suspect this disparity can be attributed to differences in life history, foraging strategies, and/or enzyme-mediated metabolism. Our results support proposing (1) the long- and short-beaked common dolphin as apex marine predator sentinels for future and retrospective biomonitoring of the SCB ecosystem and (2) the use of non-targeted contaminant analyses to identify and prioritize emerging contaminants. The use of a sentinel marine species together with the non-targeted analytical approach will enable a proactive approach to environmental contaminant monitoring.

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB) and chlordane compounds (CHLs) were determined in the blubber of males (20–25 years old) of Antarctic minke whales, Balaenoptera bonaerensis , from the International Whaling Commission (IWC) management Areas IV (70°–130°E) and V (130°E–170°W), south 60°S. The ranges of concentrations (ng g −1 lipid wt.) for each compound were, PCBs: 7.7–89; DDTs: 29–340; HCHs: 0.20–4.3; HCB: 75–430; CHLs: 10–120, which were much lower than those in common minke whales, Balaenoptera acutorostrata , from the northern hemisphere. The levels of PCBs, HCHs, HCB and CHLs in Area IV were significantly higher than those in Area V, while the levels of DDTs in both areas were similar. For comparing the fate among four pesticides in the Antarctic Ocean avoiding the effect of variance due to food intake, the ratios of the pesticides to PCBs, which has an extremely high chemical stability and environmental persistence, were examined. The HCHs/PCBs ratio decreased by a factor of about 20 in a span of 16 years in both Areas IV and V, while temporal trends of DDTs/PCBs, HCB/PCBs and CHLs/PCBs ratios were not observed. These results indicate that PCBs, DDTs, HCB and CHLs levels did not vary or slightly decreased in Areas IV and V during the study period. However HCHs levels clearly decreased. Spatial differences seems to be related to differences in food intake among whales, and temporal differences seems to be related to the length stay of OCs in the Antarctic Ocean.

Blubber from Faroese pilot whales (Globicephala melas) was analysed for brominated dioxins PBDD/Fs, with a subset also analysed for chlorinated dioxins, PCDD/Fs. The studied individuals were restricted to juvenile male whales sampled in the Faroe Islands during the period 1997-2013. Among the PBDD/Fs, the furans were predominant, although the relative abundance of various congeners differed between samples. Furans accounted for, on average, 79% of the ∑PBDD/Fs in the samples, with 1,2,3,4,6,7,8-HpBDF the most abundant congener, found in half of the analysed pilot whales. The concentration range for ∑PBDD/Fs among the samples was 0.080-71 pg/g l.w. (lipid weight), and the sum of toxic equivalents ranged from 0.0039 to 4.7 pg TEQ/g l.w. No relationship was found between PBDD/Fs and PCDD/Fs. In addition, 20 pilot whale samples from the period 2010-2013 were analysed for PBDEs. Several PBDE congeners were found in all of the sampled pilot whales, and at noticeably higher levels than PBDD/Fs and PCDD/Fs. The ∑PBDEs ranged from 140 to 1900 ng/g l.w., with BDE #47 the most abundant congener detected in the samples. Results from the present study were then compared with data from previous studies on pilot wales to investigate temporal trends between 1986 and 2013. The comparison indicated that PBDE concentrations in juvenile males have decreased from 1996 to the latest observations in 2013. No relationship between the concentration levels of PBDD/Fs and PBDEs in the sampled pilot whales could be identified, which indicates possible differences in the metabolism of, or exposure to, PBDEs and PBDD/Fs.

Blubber samples were collected from ten franciscana dolphins either incidentally captured in fishing operations or stranded on Sao Paulo (SP) and Parana (PR) states littoral, Southeastern and Southern Brazilian coast, respectively. Determination of PCB, DDT and HCB concentrations were performed by capillary gas chromatograph coupled to electron capture detector (ECD). ΣDDT, ΣPCB and HCB concentrations ranged from 264 ng g−1 to 5811 ng g−1 lipid, from 909 ng g−1 to 5849 ng g−1 lipid and from 10 ng g−1 to 61 ng g−1 lipid, respectively. Regarding DDTs, the distribution of the mean percentages decreased in the following order: p,p′-DDE > p,p′-DDD > p,p′-DDT. The ΣDDT/ΣPCB ratio varied between 0.27 and 0.42 in Northern and Central SP coast, while in Southern SP and PR coast the values were 1.6 and 1.9, respectively. Dissimilarities in ΣDDT/ΣPCB ratios point to different sources of organochlorine compounds to franciscana dolphins in the study area. Considering the endocrine disruptive action of organochlorine compounds, the concentrations found in franciscana dolphins from Brazilian waters may represent an additional obstacle to the conservation of this endangered cetacean species.

A previously unidentified yet abundant substituted polybrominated diphenyl ether (PBDE) was isolated from a northern bottlenose whale (Hyperoodon ampullatus) found dead in the Skagerrak, North Sea. A combination of gas chromatography, high and low resolution mass spectrometry and nuclear magnetic resonance spectroscopy (NMR) ((1)H, (1)H-(1)H and (1)H-(13)C) after isolation with preparative capillary gas chromatography (PCGC) lead to the identification of the unknown substance as 6-MeO-5-Me-2,2',3,4'-tetrabromo diphenyl ether (6-MeO-5-Me-BDE42). To our knowledge this is only the second time PCGC has been used to isolate individual organohalogen compounds present in trace amounts for identification with NMR. The concentration of this novel bioaccumulated compound was estimated to be about 100 ng g(-1) lipid, which was 2.5 times higher compared with the most abundant MeO-PBDE congeners.

Despite several studies that report accumulation of polychlorinated biphenyls (PCBs) and DDT in marine mammals worldwide, very few have examined polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like PCBs. In particular, no earlier studies have reported concentrations and accumulation profiles of persistent organic pollutants (POPs) in marine mammals from Korea. In this study, concentrations and accumulation features of PCDD/Fs and dioxin-like PCBs were measured in liver and blubber of minke whales and long-beaked common dolphins collected from Korean coastal waters. The concentrations of PCDFs and dioxin-like PCBs in blubber were 3-10 times higher than the concentrations measured in liver, but PCDDs were higher in liver than blubber. Total toxic equivalent (TEQ) concentrations in blubber of minke whales and common dolphins from Korean coastal waters were similar to, or higher than those reported for cetaceans and seals from other countries. Homologue and congener profiles of PCDD/Fs were different between livers and blubbers, while the profiles of dioxin-like PCBs were similar between the tissues. Concentrations of PCDD/Fs and dioxin-like PCBs in liver and blubber of dolphins were significantly higher than those measured in whales, due to differences in habitat and diet. The relative contribution of individual chemical groups to total TEQs was different between the two cetacean species, suggesting different exposures and metabolic activity. The TEQ levels in minke whales did not exceed the threshold level suggested for immunomodulation, while TEQs in all dolphin samples exceeded the suggested threshold level, implying potential adverse health effects from exposure to PCDD/Fs and PCBs.

Polar bears (Ursus maritimus) feed mainly on ringed seal (Phoca hispida) and consume large quantities of blubber and consequently have one of the highest tissue concentrations of organohalogen contaminants (OHCs) worldwide. In East Greenland, studies of OHC time trends and organ system health effects, including reproductive, were conducted during 1990-2006. However, it has been difficult to determine the nature of the effects induced by OHC exposures on wild caught polar bears using body burden data and associated changes in reproductive organs and systems. We therefore conducted a risk quotient (RQ) evaluation to more quantitatively evaluate the effect risk on reproduction (embryotoxicity and teratogenicity) based on the critical body residue (CBR) concept and using a physiologically-based pharmacokinetic (PBPK) model. We applied modelling approaches to PCBs, p,p'-DDE, dieldrin, oxychlordane, HCHs, HCB, PBDEs and PFOS in East Greenland polar bears based on known OHC pharmacokinetics and dynamics in laboratory rats (Rattus rattus). The results showed that subcutaneous adipose tissue concentrations of dieldrin (range: 79-1271 ng g(-1) lw) and PCBs (range: 4128-53,923 ng g(-1) lw) reported in bears in the year 1990 were in the range to elicit possible adverse health effects on reproduction in polar bears in East Greenland (all RQs > or = 1). Similar results were found for PCBs (range: 1928-17,376 ng g(-1) lw) and PFOS (range: 104-2840 ng g(-1) ww) in the year 2000 and for dieldrin (range: 43-640 ng g(-1) lw), PCBs (range: 3491-13,243 ng g(-1) lw) and PFOS (range: 1332-6160 ng g(-1) ww) in the year 2006. The concentrations of oxychlordane, DDTs, HCB and HCHs in polar bears resulted in RQs

The aim of this study was to investigate levels of some major environmental contaminants, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and organochlorine pesticides in Antarctic samples. Concentrations of some persistent organic pollutants (POPs) were investigated in Antarctic fur seal pups and eggs of three species of penguins. Dichloro-diphenyl-trichloroethane (DDT) was the main pollutant, followed by PCBs; other organochlorine compounds such as hexachlorobenzene (HCB) and PCDD/Fs were usually found only in minor quantities. Adélie penguin eggs had significantly higher mean PCB concentrations (p0.05) compared to the other two penguin species, but there was no difference in DDT levels (p0.05). TEQ values in fur seal blubber in our study were one order of magnitude lower than those considered to elicit physiological effects in aquatic mammals. In general, POP concentrations in our samples suggested that likely the study populations were not currently at risk for adverse health effects, but indicated a clear need for further monitoring to assess the presence and time trend of a broad range of contaminants, mainly emerging POPs thought to be increasing in polar regions.

Seven pairs of southern elephant seals (Mirounga leonina) pups and their dams were sampled during the late weaning season among a breeding population of seals on Elephant Island in Antarctica. The blubber of the pups and the milk and blubber of their dams were analyzed for lipid-normalized concentrations of PCBs and organochlorines compounds in order to evaluate the lactational transfer of these contaminants. The lipid-normalized concentrations in these tissues were in the ppb range (i.e., ngg(-1) lipid). The levels of contaminants in southern elephant seals were low in comparison with residues that have been reported in pinnipeds from the northern hemisphere. The relative tissue concentrations of the analytes measured followed the pattern: SigmaDDT>mirex>SigmaPCB>Sigmachlordane>HCB>heptachlor epoxide>dieldrin>methoxychlor>SigmaHCH>other organochlorines. The very high DDE/SigmaDDT ratio (0.91) in the blubber of dams and pups was an indicative of long-term, extremely distant pollution. On the other hand, the relatively high levels of some other organochlorine pesticides (e.g. mirex, heptachlor epoxide, dieldrin, methoxychor) may reflect the continued use of these insecticides in developing countries located in the southern hemisphere. For most of the analytes measured, the lipid-normalized concentrations were lower in pup blubber and in the milk than in the maternal blubber. Lactational transfer rates were dependent on the logK(ow) (octanol/water partition coefficient) values of the analytes measured, less lipophilic compounds being more readily transferred to the pups by the lactational route.

The halogenated natural product previously named mixed-halogenated compound 1 (MHC-1) was isolated from the red seaweed Plocamium cartilagineum harvested in Helgoland, Germany. A total of 1.9 mg of pure MHC-1 was obtained from 1g air-dried seaweed. The 1H and 13C NMR data matched those reported for a natural monoterpene isolated from this species. Thus, the structure of MHC-1 was established to be (1R,2S,4R,5R,1'E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(2'-chloroethenyl)-5-methylcyclohexane. Moreover, the isolated monoterpene proved to be identical with the compound previously detected in marine mammals and fish from different locations. In addition we examined two samples of P. cartilagineum from Ireland and from the Antarctic; however MHC-1 was only present at low levels. Not only the concentrations were lower but also the pattern of polybrominated compounds differed from MHC-1. A calibrated solution of MHC-1 was used to determine correct concentrations from samples where previously only estimates existed relative to the gas chromatography-electron capture detector (GC/ECD) response of trans-chlordane, which underrated the MHC-1 concentrations by more than factor 2. The highest MHC-1 concentration determined to date in marine mammals is 0.14 mg kg(-1) blubber. Significantly higher MHC-1 concentrations were determined in farmed fish with up to 2.2 mg kg(-1) lipids. The samples with high concentrations of MHC-1 have in common that they were collected in proximity of the natural habitats of P. cartilagineum.

The effects of persistent organic pollutants on renal and liver morphology in farmed arctic fox (Vulpes lagopus) were studied under experimental conditions. Control animals received a diet containing pork (Sus scrofa) fat with low amounts of persistent organic pollutants, while the diet of the exposed animals contained whale blubber, 'naturally' contaminated with persistent organic pollutants. Polychlorinated biphenyls (PCB) and organochlorine pesticide (OCP) concentrations in the whale blubber were 488 and 395 ng/g wet weight, respectively. Animals were sacrificed and sampled when they were at their fattest (winter) as well as their lowest body weight (summer). The results show that PCB and OCP exposure causes renal (and probably also liver) lesions in arctic foxes. The prevalence of glomerular, tubular and interstitial lesions was significantly highest in the exposed group (chi-square: all p0.05). The frequency of liver lesions (steatosis, intravascular granulocyte accumulations, interstitial cell infiltrations, lipid granulomas, portal fibrosis and bile duct hyperplasia) were also highest in the exposed group, although not significantly (chi-square: all p0.05). The prevalence of lesions was not significantly different between lean (winter) and fat (summer) foxes for any of the lesions (chi-square: all p0.05). We suggest that wild arctic foxes exposed to an environmental cocktail of persistent organic pollutants, such as PCBs and OCPs, in their natural diet are at risk for developing chronic kidney and liver damage. Whether such lesions may have an impact on age and health of the animals remains uncertain.

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-b-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-b-cyclodextrin/SE52 (1:4) for the metabolites, respectively. � 2006 Elsevier Ltd. All rights reserved.

We collected blubber samples from bottlenose dolphins stranded on Spain's Mediterranean coasts over a 25-year period (1978-2002). Samples were analyzed to determine time trends in levels of: HCB (hexachlorobenzene), PCB (polychlorinated biphenyls) and tDDT (dichlorodiphenyltrichloroethane and its metabolites). Overall, levels were high relative to other areas. This reflects both the ubiquity of organochlorine pollution in the western Mediterranean and the sampled species' coastal habit. There was a significant decline over the study period in the concentrations of all the compounds analyzed. However, the DDE/tDDT, which is indicative of DDT ageing, significantly increased. This suggests there has been no significant use of HCB, DDT or PCB in the region for a long time. It also indicates that the pollutant loads in the environment are gradually being reduced; either by degradation or by migration of the compounds to other regions. A comparison with dolphin species that have an oceanic distribution suggests that PCB decline at a comparable pace in coastal and offshore water bodies. However, the decline of tDDT is faster near the coast.

As a marine mammal species that inhabits shallow nearshore waters, humpback dolphins are likely exposed to a wide range of pollutants from adjacent land-based activities. Increased mortality rates of Australian humpback dolphins (Sousa sahulensis) in waters off a major urbanised centre triggered investigations into the threats to these species, including their contaminant exposure. The present study utilised archived tissues from 6 stranded animals to screen for a range of pollutants (PCDD/Fs, PBDEs, PCBs, organochlorine pesticides, PAHs, organotins, essential and non-essential elements) to inform future biopsy based biomonitoring strategies. Concentrations of PCBs and DDXs in blubber of some of these animals were remarkably high, at levels near or above toxicological thresholds associated with immune- and reproductive toxicity or population declines in other marine mammals. PBDEs, PAHs, HCB, organotins, 'drins' as well as other organic pesticides were not detected, or present at relatively low concentrations. Profiles of elements were similar in epidermis compared to other tissues, and apart from some exceptions (e.g. Fe, Cr, Co, Cu) their concentrations fell within 25th-75th percentiles of cetacean baselines in four of the five animals. Non-essential elements (Al, V, Pb, Ba, Ni, Cd) were notably elevated in one specimen which may have experienced poor health or nutritional status. These data provide a first insight into the contaminant status of a rare and poorly studied population inhabiting an urbanised area. The results highlight a need for future biomonitoring of live populations, and inform on priorities in the typically limited blubber and skin sample volumes obtained through biopsies.

Cetaceans hunted coastally in Japan include several species of odontocete (dolphins, porpoises and beaked whales), and fresh and frozen red meat and blubber, as well as boiled internal organs, such as liver, lung, kidney and small intestine, are still sold for human consumption. Furthermore, red meat and blubber products originating from mysticete minke whales caught in the Antarctic and Northern Pacific are also sold for human consumption. We surveyed mercury and cadmium contamination levels in boiled liver, lung, kidney and red meat products being marketed in Japanese retail outlets. We also analyzed the DNA of these products to obtain information concerning gender and species. Total mercury (T-Hg) and methyl mercury (M-Hg) contamination levels in all the cetacean products were markedly higher in odontocete species than in mysticete species, and slightly higher in females than in males. T-Hg contamination in the organs was seen in the following order: boiled liver > boiled kidney=boiled lung > red meat. In particular, T-Hg concentrations in the boiled liver were high enough to cause acute intoxication even from a single ingestion: the mean ±SD (range) of T-Hg was 388 ± 543 (0.12–1980) μg/wet g. In contrast, although M-Hg contamination in the liver was not markedly higher than that in other organs, M-Hg contamination was in the following order: boiled liver > odontocete red meat > boiled kidney > boiled lung. The contamination levels of T-Hg and M-Hg in odontocete red meat, the most popular whale product, were 8.94 ± 13.3 and 5.44 ± 5.72 μg/wet g, respectively. These averages exceeded the provisional permitted levels of T-Hg (0.4 μg/wet g) and M-Hg (0.3 μg/wet g) in marine foods set by the Japanese Ministry of Health, Labor and Welfare by 22 and 18 times, respectively, suggesting the possibility of chronic intoxication by T-Hg and M-Hg with frequent consumption of odontocete red meat. Cadmium contamination levels in boiled liver, kidney and lung were 8.59 ± 12.0, 10.4 ± 8.6 and 1.66 ± 1.27 (μg/wet g), respectively.

Blubber and skin samples from 63 spotted dolphins ( Stenella attenuata ) (18 males, 40 females and 5 of unknown sex) were collected by biopsy techniques in the waters of the Coiba archipelago. Blubber was analyzed for organochlorine compounds and skin for gender determination. Mean levels of HCB (hexachlorobenzene), tPCB (polychlorinated biphenyls) and tDDT (dichlorodiphenyltrichloroethane) were 0.064, 2.30 and 6.4 mg kg −1 , respectively. These levels are low and are not considered to represent a threat to the S. attenuata population. No significant differences either in concentrations of HCB, tPCB and tDDT or in PCB profiles were observed between males and females. The ratio tDDT/tPCB was 2.69, indicating predominantly agrarian versus industrial activities in the area. The ratio ppDDE/tDDT was 0.83, a high figure that suggests both a local reduction of DDT inputs and a high rate of DDT degradation. Significant quantitative and qualitative differences were observed between two schools, suggesting intra-population heterogeneity in organochlorine exposure possibly due to demographic segregation.

This presentation adds new spectroscopic and analytical data on the natural product Q1 that was recently identified by synthesis as 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole. Solid state magic angle spinning 13C NMR data of Q1 is presented as an option for structural proof. Furthermore, the UV spectrum of neat Q1 (absorption maximum at 223 nm) was recorded and, with NMR spectroscopic data, confirmed a twisted bipyrrole ring system. A quantitative standard of Q1 was prepared which allowed to correct previous concentration estimates relative to the electron capture detector response factor of trans-nonachlor. As a result, the actual Q1 response was only 0.65+/-15% of the response factor of trans-nonachlor. Therefore, actual Q1 levels are about 50% higher than the previous estimates. With this result the highest (corrected) Q1 concentration determined to date in the blubber of marine mammals from Australia is 14 mg/kg lipid. Analysis of Q1 and trans-nonachlor in specimens from the German North Sea coast suggests that harbor seals are more able to metabolize Q1 than harbor porpoises. Finally, we calculated that 79 congeners of Q1 (i.e. lower chlorinated 1(')-methyl-1,2(')-bipyrroles) are theoretically possible and present their structures.

Several identified and potential natural brominated bioaccumulative compounds were studied in this work. 4,6-dibromo-2-(2('),4(')-dibromo)phenoxyanisole (BC-2) previously detected in Australian marine mammals and isolated from sponges, was synthesized. Two byproducts (a tetrabromo isomer and a tribromo congener) were investigated as well. The byproducts of the synthesis were not identified in the environmental samples investigated. Previously described natural brominated compounds (BC-1, BC-2, BC-3, BC-10, BC-11, MHC-1) and anthropogenic brominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-154) were detected in a sample of human milk. The sample was from a woman from the Faeroe Islands who frequently consumed fish as well as whale blubber and meat. The most abundant compound originated from the natural tetrabromo phenoxyanisole BC-3 which may have a 3:1 distribution of bromine on the two phenyl units. This sample also accumulated a dibromochloroanisole, as well as a previously unknown mixed halogenated compound (MHC-X) and an unknown, most likely aromatic brominated compound. Co-elutions on a DB-5 column were found for BDE-99 and BC-11 as well as BDE-154 and the unknown brominated compound. This suggests that quantification of these two compounds has to be carried out carefully.Two samples of lower trophic level, namely Baltic cod liver and Mexican mussel tissue, were investigated as well. The cod liver samples contained BDE congeners but also abundant signals for the natural 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole Q1 and tribromoanisole (TBA). The mussel sample contained Q1, TBA, another halogenated anisole, BC-1, BC-2, and BC-3, as well as additional, potential natural brominated compounds in the elution range of tribromophenoxyanisoles.

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis - and trans -chlordane, heptachlor exo -epoxide, oxychlordane, U82, MC5, MC6, MC7, o , p ′ -DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.

To explore the levels of polybrominated diphenyl ethers (PBDEs) in California, samples from 11 archived harbor seals (Phoca vitulina Richardsi) from the San Francisco Bay and breast adipose tissue samples from 23 women were analyzed. The levels of PBDEs in human tissue samples were in the low ng/g fat range, with PBDEs 47, 153, 154, 99, and 100 as the major congeners. Average sigma PBDEs (86 ng/g fat) in these California women are the highest human levels reported to date. An inverse relationship between concentration of PBDEs and age of these women was apparent. The levels of PBDEs measured in harbor seal blubber were in the low ng/g to low microg/g fat range, with the same major congeners as those measured in the human tissues. PBDE 47 was the highest among all congeners measured in both human tissue and seal blubber samples. The concentrations of PBDEs in harbor seals in the San Francisco Bay have increased dramatically over the past decade, with current levels among the highest reported for this species.

The aim of the present study was to measure polycyclic aromatic hydrocarbon (PAH) levels in free-ranging Mediterranean cetaceans as they are likely to cause chemical stress in the organisms of this basin. Blubber samples were collected from live specimens of fin whales (Balaenoptera physalus) and striped dolphins (Stenella coeruleoalba) by means of biopsies, a non-destructive biological method. Fin whales were sampled in the Ligurian Sea, whereas striped dolphins were collected in the Ligurian and the Ionian Seas. A fingerprint of 14 PAHs was obtained for both species. In whales, the median value of total PAHs was 1970 ppb fresh weight (f.w.) while median carcinogenic PAH values were 89.80 ppb f.w.; in dolphins, the median values of total and carcinogenic PAHs were 29,500 and 676.00 ppb f.w., respectively. The different PAH values between the two species can be attributed to the different positions they take in the Mediterranean food web. The sampling period significantly influenced PAH concentrations of fin whales.

The literature concerning persistent organic pollutants (POPs) in the environment of Greenland and the Faroe Islands covering the period up to 1995 has been revisited. It is difficult to compare data from earlier studies with those from more recent investigations. Thus as the former quantified the content of CBs by comparison to a technical mixture of CBs (e.g. Aroclor 1254), the latter analyses typically are quantified on a single congener level. Single CB congeners have in some cases been determined, but the results were subsequently expressed as total PCB related to an Aroclor standard. For studies based on single CB congener determinations, the highest levels are reported for porpoise blubber from Greenland (700-4500 micrograms/kg wet weight), the conclusion, however being based on two determinations only. In Greenlandic seal blubber and peregrine falcon plasma equal levels of CBs (130-750 micrograms/kg ww) and of DDTs (150-860 micrograms/kg ww) were found. Levels of CBs and DDTs in fish liver were found to be around 40-75 micrograms/kg ww. In sediment samples the CBs were almost all below the detection limit (< 0.02-0.1 microgram/kg dry weight), and thereby being the matrix with the lowest CBs concentration levels. Earlier data based on Aroclor standards showed DDT levels in Greenlandic whale blubber in the range of 2700-4100 micrograms/kg ww and PCB levels of 3700 micrograms/kg-5400 micrograms/kg ww. DDT levels for seal blubber were at the same level (2700-4500 micrograms/kg ww) whereas the PCB level was lower (900-3900 micrograms/kg ww). The PCB level corresponds to the level found in human adipose tissue determined with a similar quantification technique. The lowest levels reported for mammals correspond to walrus blubber, the sum of PCBs and DDTs being in the ranges of 180-360 micrograms/kg ww and 50-90 micrograms/kg ww, respectively. The content of PCBs in scallops was found to be 3 micrograms/kg ww near the Thule Air base.

Hepatic microsomal cytochrome P450, EROD and ECOD activity were investigated as biomarkers of PCB exposure in harbour seals (Phoca vitulina). Due to the difficulty of obtaining undegraded seal liver samples, standard spectrophotometric methodology was adapted to investigate P420 (degraded P450) as a PCB biomarker with partially degraded samples. Total PCB burdens in both blubber and liver had positive correlations with P450, P420 and MFO activity levels. The use of P420 biomarkers in this study supports the inclusion of samples from by-caught marine mammals for future biomonitoring studies. P450 isozymes CYP1A (P4501A) and CYP2B (P4502B) in conjunction with MFO activity were investigated as "specific" biomarkers of PCB exposure. They were found to reliably reflect levels of [MC] and [PB]-type PCB exposure in harbour seal liver.

Concentrations of chlorinated hydrocarbons (CHs), such as polychlorinated biphenyls (PCBs), were measured in subsamples taken from different anatomical locations of blubber and liver of three apparently healthy harbor porpoises (Phocoena phocoena) incidentally caught in a gill-net fishery along the northwest Atlantic coast; selected elements (e.g., mercury) were measured in subsamples of liver. The vertical distribution (skin to muscle) of contaminants within blubber was also determined. Additionally, the concentrations of CHs and elements were determined in individual samples of brain, lung, kidney, and testis to assess how the disposition of toxic chemicals may be dependent on the physiological characteristics of a specific organ. Statistical analyses of the results showed that the anatomical location of the blubber or liver sample had no significant effect on concentrations of either CHs in blubber and liver, or of selected elements in liver. However, there were statistical differences between strata of blubber (skin to muscle) for the concentrations of CHs. As expected, the results showed that the CH concentrations, based on wet weight, were considerably higher in the blubber than in the other tissues; however, the concentrations of CHs in the different tissues were more comparable when values were based on total lipid weight with the exception of the brain where lipid normalized concentrations were than in all other tissues. This low relative accumulation of lipophilic contaminants in the brain tissue may be due to the presence of the blood-brain barrier, or due to a lower proportion of neutral lipids, such as triglycerides, as analysis for percent lipid and for the proportion of specific lipid classes showed.

The U.S. National Biomonitoring Specimen Bank (NBSB) provides for the long term storage of well documented and preserved specimens representing several types of environmental matrices. A major part of this inventory consists of marine mammal tissues (e.g., blubber, liver, kidney, and muscle). Within the NBSB selected specimens are periodically analyzed for chlorinated hydrocarbons and trace elements. Although only 20% of the 560 marine mammal specimens in the NBSB have been analyzed, the database is of value in evaluating the stability of analytes and sample degradation during storage, for comparing with results from samples collected in the future for long-term monitoring, and for comparing with analytical results from other laboratories on samples collected at the same time for monitoring purposes. The NBSB analytical database contains results for 37 elements, many of which are not analyzed routinely by conventional analytical techniques used in monitoring programs, and the following organic compounds: selected PCB congeners, DDT compounds, α- and γ-HCH, HCB, heptachlor epoxide, oxychlordane, cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor, and dieldrin in 9 marine mammal species: northern fur seal ( Callorhinus ursinus ), ringed seal ( Phoca hispida ), spotted seal ( P. largha ), bearded seal ( Erignathus barbatus ), pilot whale ( Globicephala melas ), harbor porpoise ( Phocoena phocoena ), white-sided dolphin ( Lagenorhynchus acutus ), beluga whale ( Delphinapterus leucas ), and bowhead whale ( Balaena mysticetus ). Analyses of beluga whale blubber for toxaphene and additional chlorinated hydrocarbons are obtained through collaboration with the Department of Fisheries and Oceans Canada.

Indo-Pacific humpback dolphins (Sousa chinensis) are apex predators in the Pearl River Estuary waters (PRE) of China. PCBs, DDTs and other organochlorine pesticides (OCPs) (e.g., HCHs, HCB, mirex and dieldrin) were analysed in blubber samples of 45 dolphins and 10 prey fishes of S. chinensis collected from 2004 to 2013 in the PRE region to investigate the bioaccumulation and potential biomagnification of persistent organic pollutants (POPs). DDTs were the most abundant residue in the dolphins, with an average of 6,2700 ng g(-1) wet weight (ww), followed by PCBs (average: 1,790 ng g(-1) ww) and other OCPs including ∑HCHs, mirex, endrin, ∑chlordanes, HCB, dieldrin, aldrin, heptachlor, and pentachlorobenzene. The concentrations of PCBs and DDTs in male dolphins significantly increased with age and length. In contrast, female dolphins did not show obvious bioaccumulation trends with age and body length, possibly due to the lactational and parturitional transfer of these compounds. Compared with the POP residues in the prey fishes, the concentrations of PCBs, DDTs, and HCHs in the dolphin blubber increased by factors of 99, 212, and 5, respectively, whereas the residue levels of the other OCPs increased 2-185 times, indicating a potentially significant biomagnification in the top predators. The potential biomagnification factors calculated for most POPs were significantly higher than those in the cetacean species from other regions.

Physiologically based pharmacokinetic (PBPK) models for wild animal populations such as marine mammals typically have a high degree of model uncertainty and variability due to the scarcity of information and the embryonic nature of this field. Parameters values used in marine mammals models are usually taken from other mammalian species (e.g. rats or mice) and might not be entirely suitable to properly explain the kinetics of pollutants in marine mammals. Therefore, several parameters for a PBPK model for the bioaccumulation and pharmacokinetics of PCB 153 in long-finned pilot whales were estimated in the present study using the Bayesian approach executed with Markov chain Monte Carlo (MCMC) simulations. This method uses prior information of the parameters, either from the literature or from previous model runs. The advantage is that this method uses such prior parameters to calculate probability distributions to determine posterior values that best explain the field observations. Those field observations or datasets were PCB 153 concentrations in blubber of long-finned pilot whales from Sandy Cape and Stanley, Tasmania, Australia. The model predictions showed an overall decrease in PCB 153 levels in blubber over the lifetime of the pilot whales. All parameters from the Sandy Cape model were updated using the Stanley dataset, except for the concentration of PCB 153 in the milk. The model presented here is a promising and preliminary start to PBPK modeling in long-finned pilot whales that would provide a basis for non-invasive studies in these protected marine mammals.

Few natural matrix Standard Reference Materials are available for the validation of analytical methods measuring polychlorinated dioxins and furans (PCDDs and PCDFs) in marine ecosystems. The concentrations of PCDDs and PCDFs in NIST SRM 1945, SRM 1974a, and SRM 1941a are of interest because the analysis of marine mammal, mussel tissues and sediments have become important tools in the determination of organochlorine contamination of the environment. Because these SRMs have been demonstrated to be homogenous for other organic contaminants, they would be expected to be reliable standards for validation of polychlorinated dioxins and furans in marine mammals, mussels and sediments as well.

Metabolism of chlorobiphenyls (CBs) was studied in harbour porpoise by comparing patterns of CB-X/CB-153 ratios in blood, brain, liver and blubber with the patterns in herring, the main food source. The CBs were classified in five groups, based on the presence/absence of vicinal H-atoms (vic. Hs) in meta,para (m,p) and/or ortho,meta (o,m) positions and the number of ortho-Cl-atoms (ortho-Cls). Plots of CB-X/CB-153 ratios in porpoise tissue vs the ratios in herring appeared to be linear for each CB group in all tissues. Slopes of these plots (metabolic slopes) were used as quantitative indicators of metabolic activity. In this way, activity of PB-type isozymes of the P450 monooxygenase system was apparent: in contrast to existing literature data, harbour porpoise appears to be able to metabolize congeners with m,p vic. Hs, even in the presence of more than 2 ortho-Cls. The presence of 3-MC-type (MC-type) isozymes was also detected. The metabolic slopes were also used as basis for risk assessment. Due to their metabolism the most toxic non-ortho CBs were not present in the tissues at detectable levels. We suggest a risk assessment approach which takes this into account. It is considered to be an alternative and more reliable basis for risk assessment than the use of toxic equivalent factors. The results support the model of equilibrium distribution of CBs in harbour porpoise and the role of blood as central transport medium. The model has been developed for persistent compounds; it appears to hold for metabolizable CB congeners as well.

Residues of DDT and its metabolites, hexachlorocyclohexanes (HCHs), chlordane, toxaphene, polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) were determined by GC ECD and GC MS in the blubber of a seal (Phoca caspica) from the coast of Iran on the Caspian Sea. The organochlorine pattern was dominated by DDT and its metabolites while PCBs (65 PCB congeners including non-ortho PCBs were quantified) only played a minor role. The high content of β-HCH determined by GC ECD and confirmed by GC MS was interpreted to be caused by local sources. On the other hand, residues of chlordane compounds were correlated to atmospheric long-range transport.

As part of a study examining the possible effects of organochlorine compounds on juvenile northern elephant seals (Mirounga angustirostris), blubber and blood samples were taken from animals present on the Año Nuevo (California) rookery, and from animals admitted for rehabilitation at The Marine Mammal Center (Sausalito CA). Blubber samples were collected from immobilized seals. A pre-cleaned 6 mm K-medic biopsy punch was used to extract the blubber from a 1 cm incision near the hip, near the dorsal mid point. Blood samples were taken from the extradural vein; two mL of serum was analyzed for organochlorine compounds. Blubber samples (approximately 0.1g) were ground with Na2SO4 and extracted with 20 mL hexane:methylene chloride (1:1). Sera samples were extracted using commercially available disposable C18 columns. The extracts were separated on a micro-Florisil column, and analyzed by HRGC-ECD. Lipid determination in the serum was obtained by colorimetric analysis with 20 microliters samples. Results from the analysis of replicates and standard reference materials showed good recoveries, precision, and accuracy for both the blubber and blood methods.

Bottlenose dolphins ( Tursiops truncatus ) collected during the 1987/88 mass mortality event along the Atlantic coast of the United States have been analyzed for coplanar PCBs #77, 105, 126 and 169 in blubber, and for the metals Hg, Pb, Cd, Mn, and Cr, and the non-metallic element Se in liver. Results have been compared to two reference species, common ( Delphinus delphis ) and white-sided ( Lagenorhynchus acutus ) dolphins. The three most toxic PCB congeners (#77, 126 and 169) contributed less than 1% of the total TCDD toxic equivalent concentration (TEC) calculated for all di-, mono- and non-ortho chlorine substituted PCBs in adult male animals. The total TEC for the four PCBs was approximately 4.5 times lower in adult female bottlenose than in male. The mean concentrations of Pb, Cd, Mn and Cr in adult male bottlenose dolphins were at or below the mean concentrations in the two reference species. The mean concentration of mercury was highest in adult female bottlenose dolphins. However, mercury concentrations in all animals studied correlated with selenium concentrations (r=0.86) at a 1:1 mole ratio, indicating that selenium may protect these animals from mercury toxicity.

Stationary phases based on dimethyl-t-butylsilylated heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin diluted with different polysiloxanes were developed for the enantiomer separation of chiral toxaphene congeners by high resolution gas chromatography (HRGC). They allowed to determine the enantiomer ratio of an octa- and nonachloro congener isolated from seal blubber. The found ratios of 1,024 and 1,059 were very close to those of the racemates and indicate that enantiomer selective metabolisation is not significant in seals. Furthermore, the enantiomer separation of 11 racemic toxaphene congeners obtained by synthesis was also performed. Two of them had the same retention times as the isolated congeners on 3 or 5 stationary phases, respectively, and similar negative ion chemical ionisation mass spectra. First attempts are made to explain differences in the observed enantiomer separations by the steric structure of the congeners. In addition, general aspects and difficulties of enantiomer selective separations by HRGC are discussed.

The aim of the present study was to examine the possibilities of using blood as a matrix for determining exposure to organochlorine compounds in seal pups, and to elucidate the possible correlations between pollutant load and biological variables. The mean values of ∑PCB and ∑DDT in blood cells of 17 live grey seal ( Halichoerus grypus ) pups from Froan, Norway, were 4.59 (SD = 7.61, n = 17), and 3.38 ng/g wet weight (SD = 4.74, n = 17), respectively. If calculated on lipid weight basis, the contents of ∑PCB and ∑DDT were 2819.6 (SD = 2956.7, n = 17) and 1982.3 ng/g l.w. (SD = 2013.7, n = 17), respectively, and similar to mean values reported in blubber tissue of dead seal pups from the same area. The data indicate that the concentrations of ∑PCB and ∑DDT in neonatal pups at Froan are lower as compared to concentrations reported in blood of grey seal pups from the Northwest Atlantic. Although the two pups that had the highest ∑PCB concentrations also had the lowest plasma concentrations of thyroxine, there was no significant correlation between the ∑PCB concentration in blood cells and the corresponding plasma concentrations of any of the thyroid hormones. We conclude that blood-sampling is a suitable non-destructive method for monitoring organochlorine residues in seals.

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in blubber biopsy samples from 22 live-captured Steller sea lions (Eumetopias jubatus) that had just entered the Strait of Georgia, British Columbia, Canada, for their overwintering feeding season. ∑PBDE ranged from 50μgkg(-1) (lipid weight) in adult females to 3780μgkg(-1) in subadult individuals. ∑PCBs ranged from 272μgkg(-1) in adult females to 14280μgkg(-1) in subadult individuals. While most PBDE and PCB congeners were transferred through milk to pups, PCBs with logK(OW)7.0 (PCBs 206, 207, 208 and 209) appeared constrained, resulting in a lighter mixture in pups compared to adult females. The ratio of individual PCB congeners by metabolic group (Groups I, II, III, IV and V) to PCB-153 regressed against length of males suggested poor biotransformation of these compounds (slopes did not differ from zero, p0.05). PBDE congeners 49, 99, 153 and 183 appeared bioaccumulative (slopes of ratio BDE/PCB 153 versus length were higher than zero, p0.05), but the dominance of the single congener, BDE-47 (64% of total PBDEs), likely due in part to debromination pathways, reduced our ability to explore congener-specific dynamics of PBDEs in these pinnipeds. With 80% of our Steller sea lions exceeding a recent toxicity reference value for PCBs, the fasting-associated mobilization of these contaminants raises concerns about a heightened vulnerability to adverse effects during annual migrations.