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Lipophilic persistent organic pollutants (POPs) tend to biomagnify in food chains, resulting in higher concentrations in species such as killer whales ( Orcinus orca ) feeding on marine mammals compared to those consuming fish. Advancements in dietary studies include the use of quantitative fatty acid signature analysis (QFASA) and differentiation of feeding habits within and between populations of North Atlantic (NA) killer whales. This comprehensive study assessed the concentrations of legacy and emerging POPs in 162 killer whales from across the NA. We report significantly higher mean levels of polychlorinated biphenyls (PCBs), organochlorine pesticides, and flame retardants in Western NA killer whales compared to those of Eastern NA conspecifics. Mean ∑PCBs ranged from ∼100 mg/kg lipid weight (lw) in the Western NA (Canadian Arctic, Eastern Canada) to ∼50 mg/kg lw in the mid-NA (Greenland, Iceland) to ∼10 mg/kg lw in the Eastern NA (Norway, Faroe Islands). The observed variations in contaminant levels were strongly correlated with diet composition across locations (inferred from QFASA), emphasizing that diet and not environmental variation in contaminant concentrations among locations is crucial in assessing contaminant-associated health risks in killer whales. These findings highlight the urgency for implementing enhanced measures to safely dispose of POP-contaminated waste, prevent further environmental contamination, and mitigate the release of newer and potentially harmful contaminants.

Temporal trends of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) were examined in blubber samples of 50 finless porpoises (Neophocaena phocaenoides) and 25 Indo-Pacific humpback dolphins (Sousa chinensis) collected from the South China Sea between 2004 and 2014. Elevated levels of SCCPs and MCCPs were detected in all blubber samples of both cetacean species. Concentrations of SCCPs ranged from 280 to 3900 ng·g-1 dry weight (dw) in porpoises and from 430 to 9100 ng·g-1 dw in dolphins, while concentrations of MCCPs ranged from 320 to 8600 ng·g-1 dw in porpoises and from 530 to 23?000 ng·g-1 dw in dolphins. Significantly higher concentrations were present in dolphins than porpoises due to their exposure levels in their living habitats. Strongly linear correlations existed between SCCPs and MCCPs, but there were no significant concentration differences between the genders of the two cetacean species in the same sampling year. Significantly temporal increasing trends of ?SCCPs and ?MCCPs have been observed in both porpoise and dolphin samples over the past decade, which reflect the influence of histories of production and usage on the bioaccumulation of CPs in marine mammals in China. An apparent temporal shift trend from SCCPs to MCCPs was also observed in CP accumulation profiles. Complex environmental fractionation from localized sources in the study region via atmospheric transport, oceanic/offshore water transport, and trophic transfer have resulted in different CP accumulation levels and homologue patterns in the two cetacean species. This is the first report of systematic temporal trends of SCCPs and MCCPs in marine mammals. [ABSTRACT FROM AUTHOR]

Quantification of bioaccumulative contaminants in biota is time and cost-intensive and the required extensive cleanup steps make it selective toward targeted chemical groups. Therefore tissue extracts prepared for chemical analysis are not amenable to assess the combined effects of unresolved complex mixtures. Passive equilibrium sampling with polydimethylsiloxane (PDMS) has the potential for unbiased sampling of mixtures, and the PDMS extracts can be directly dosed into cell-based bioassays. The passive sampling approach was tested by exposing PDMS to lipid-rich tissue (dugong blubber; 85% lipid) spiked with a known mixture of hydrophobic contaminants (five congeners of tetra- to octachloro-dibenzo-p-dioxins). The equilibrium was attained within 24 h. Lipid-PDMS partition coefficients (Klip-PDMS) ranged from 20 to 38, were independent of hydrophobicity, and within the range of those previously measured for organochlorine compounds. To test if passive sampling can be combined with bioanalysis without the need for chemical cleanup, spiked blubber-PDMS extracts were dosed into the CAFLUX bioassay, which specifically targets dioxin-like chemicals. Small quantities of lipids coextracted by the PDMS were found to affect the kinetics in the regularly applied 24-h bioassay; however, this effect was eliminated by a longer exposure period (72 h). The validated method was applied to 11 unspiked dugong blubber samples with known (native) dioxin concentrations. These results provide the first proof of concept for linking passive sampling of lipid-rich tissue with cell-based bioassays, and could be further extended to other lipid rich species and a wider range of bioanalytical end points. [ABSTRACT FROM AUTHOR]

Time trends of hexabromocyclododecane (HBCD) isomers were studied for glaucous gull and ringed seal from East Greenland. The ringed seal results extended a previous time trend (1986-2008) to 2010. α-HBCD was the only isomer consistently above quantification limits. For glaucous gull liver, annual median values of α-HBCD (1994-2010) ranged from 22 to 120 ng/g lipid weight (lw) with no significant trend, while HBCD in ringed seal blubber from the same area showed a significant increase from 3.9 to 11 ng/g lw (1986-2010). Reasons for this difference are unknown, but might include different feeding habits and species-specific metabolisation processes. Concentrations of several organochlorine (OC) compounds were determined for glaucous gull and ringed seal samples collected from the same area in 2004. HBCD concentrations in glaucous gull liver appeared relatively low when compared to OC concentrations in the same tissue and to both HBCD and OCs in ringed seal blubber from the same area. Enantiomer fractions (EF) deviated significantly from racemic for all annual mean EFs in glaucous gull suggesting metabolisation processes toward an enrichment of (−)α-HBCD. For ringed seal, this enrichment was less pronounced and only significant for two of the ten years. For neither species, significant changes in EF were found over time. [ABSTRACT FROM AUTHOR]

Analytical methods for contaminant monitoring are generally targeted; i.e., they measure defined lists of compounds. Routine monitoring projects using targeted methods are not usually designed to screen for unrecognized or novel contaminants and therefore miss compounds within the region or population of study that cause, or have the potential to cause, adverse biological impacts. We describe a nontargeted analytical method utilizing direct sample introduction coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. To test the capabilities of this instrumental method within the context of marine contaminant surveys, we characterized a broad array of nonpolar, persistent, and bioaccumulative contaminants in Atlantic common dolphin (Delphinus delphis) blubber, including compounds that are not typically monitored. Compound identifications were made by searching a standard reference database, by contemporaneously analyzing mass spectra from reference standards, and by de novo interpretation. We identified a total of 271 compounds belonging to 24 classes; all compounds but 1 were halogenated. Anthropogenic contaminants and halogenated natural products were concurrently detected. A total of 86 compounds were anthropogenic contaminants that are not routinely targeted in environmental surveys, and 54 compounds were halogenated natural products. A total of 112 spectra were identified de novo, demonstrating that exclusive reliance on commercially available reference standards and mass spectral libraries may miss a significant fraction of identifiable compounds. We also cataloged 27 halogenated mass spectra that were not able to be identified. Due to the volume and complexity of the identification data, we developed custom software to organize and provide shared access to the identified mass spectra and related information. The nontargeted analytical method and data reporting system, in combination with the analysis of a high-trophic-level sentinel species, demonstrates a framework for creating an inventory of persistent and bioaccumulative contaminants in marine environments, with the future goal of suggesting new compounds for further investigation by targeted monitoring and risk assessment. [ABSTRACT FROM AUTHOR]

Persistent organic pollutants (POPs) including legacy POPs (PCBs, chlordanes, mirex, DDTs, HCB, and dieldrin) and polybrominated diphenyl ether (PBDE) flame retardants were determined in 300 blubber biopsy samples from coastal and near shore/estuarine male bottlenose dolphins (Tursiops truncatus) sampled along the U.S. East and Gulf of Mexico coasts and Bermuda. Samples were from 14 locations including urban and rural estuaries and near a Superfund site (Brunswick, Georgia) contaminated with the PCB formulation Aroclor 1268. All classes of legacy POPs in estuarine stocks varied significantly (p < 0.05) among sampling locations. POP profiles in blubber varied by location with the most characteristic profile observed in bottlenose dolphins sampled near the Brunswick and Sapelo estuaries along the Georgia coast which differed significantly (p < 0.001) from other sites. Here and in Sapelo, PCB congeners from Aroclor 1268 dominated indicating widespread food web contamination by this PCB mixture. PCB 153, which is associated with non-Aroclor 1268 PCB formulations, correlated significantly to human population indicating contamination from a general urban PCB source. Factors influencing regional differences of other POPs were less clear and warrant further study. This work puts into geographical context POP contamination in dolphins to help prioritize efforts examining health effects from POP exposure in bottlenose dolphins. [ABSTRACT FROM AUTHOR]

Concentrations of hexabromocyclododecane (HBCD) were determined in a combination of archived and fresh blubber samples of juvenile ringed seals from East Greenland collected between 1986 and 2008. α-HBCD was the only diastereoisomer consistently above levels of quantification and showed a significant log-linear (exponential) increase from 2.0 to 8.7 ng/g lipid weight (median concentrations) with an annual rate of +6.1%. The concentrations were up to several orders of magnitude lower than those reported for marine mammals from industrialized areas. Previously presented time trends on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) have been extended with new data for 2006 and 2008. ΣPBDE in juvenile seals was the only parameter with a slight upward trend, however, dependent on the low 1986 concentration. Removing this data point resulted in a downward trend, which also was found for adult seals with a time trend starting in 1994. ΣPCB decreased significantly in juvenile seals, again due to the 1986 value, while no trend was found for the adult animals. This indicates stagnating PCB concentrations at a relatively high level, in some cases possibly exceeding tolerable daily intake rates for seal blubber as traditional Arctic food items. [ABSTRACT FROM AUTHOR]

Halogenated 1'-methyl-1,2'-bipyrroles (MBPs) are putative marine natural products that accumulate in marine mammal blubber in similar concentrations and patterns to biomagnifying organic pollutants. Here we measure concentrations of MBPs and 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153) in 40 samples composed of eight fish species, two squid species, and six species of marine mammals. To determine their trophic positions and to further investigate influence of prey preference, we also measured the stable carbon and nitrogen isotopic compositions of all samples. Our results show that lipid-normalized MBP concentrations increase with increasing trophic level; therefore, MBPs qualify as another class of biomagnifying marine natural products. The presence of MBPs in pinniped prey and absence in pinniped blubber suggests that these mammals share dietary exposure to MBPs with odontocetes but have an enhanced ability to metabolize these natural products. [ABSTRACT FROM AUTHOR]

Biomonitoring surveys of wild cetaceans commonly utilize blubber as a means to assess exposure to persistent organic pollutants (POPs), but the relationship between concentrations in blubber and those in blood, a better indicator of target organ exposure, is poorly understood. To define this relationship, matched blubber and plasma samples (n = 56) were collected from free-ranging bottlenose dolphins (Tursiops truncatus) and analyzed for 61 polychlorinated biphenyl (PCB) congeners, 5 polybrominated diphenyl ether (PBDE) congeners, and 13 organochlorine pesticides (OCPs). With the exception of PCB 209, lipid-normalized concentrations of the major POPs in blubber and plasma were positively and significantly correlated (R² = 0.828 to 0.976). Plasma concentrations, however, significantly increased with declining blubber lipid content, suggesting that as lipid is utilized, POPs are mobilized into blood. Compound- and homologue- specific blubber/blood partition coefficients also differed according to lipid content, suggesting POPs are selectively mobilized from blubber. Overall, these results suggest that with the regression parameters derived here, blubber may be used to estimate blood concentrations and vice versa. Additionally, the mobilization of lipid from blubber and concomitant increase in contaminants in blood suggests cetaceans with reduced blubber lipid may be at greater risk for contaminant-associated health effects. [ABSTRACT FROM AUTHOR]

Controls were placed on the production and use of the pentamix polybrominated diphenyl ether (PBDE) formulation within the European Union in 2004. In porpoises stranded or bycaught around the U.K., BDE congeners from this product predominate. Lipid-normalized concentrations of 9 (summed) BDE congeners in the blubber of 415 porpoises sampled during the period 1992-2008 have been investigated for possible time trends resulting from the regulatory action. Our analysis suggests that overall, median Σ9BDE concentrations peaked around 1998 and have since reduced by between 53.8% and 73.5% to 2008. Our best point estimate is that the reduction has been 67.6%. This decline was highly statistically significant (p < 0.001) and was not confounded by a range of other factors which were also considered (area, season, nutritional status, bycaught/stranded, and age class). [ABSTRACT FROM AUTHOR]

Concentrations of hexabromocyclododecanes (HBCDs), polybrominated diphenyl ethers (PBDEs), and three novel flame retardants, namely 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), bis-(2-ethylhexyl)-tetrabromophthalate (TBPH), and hexachlorocyclopentadienyldibromocyclooctane (HCDBCO), were determined in blubber samples of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides). The levels of HBCDs and PBDEs in cetacean samples ranged from 4.1 to 519 and 103 to 51,100 ng/g lw, respectively. A significant increasing trend of ΣHBCDs was observed in dolphin samples from 1997 to 2007 with an estimated annual rate of 5%, whereas no significant temporal trends of ΣPBDEs appeared over the sampling period. This pattern may be attributed to the increasing usage of HBCDs following the restriction/voluntary withdrawal of the production and use of PBDE commercial mixtures in several countries. HCDBCO was not found in the blubber samples. This is the first report of the presence of TBB and TBPH, two new flame retardants that have previously been identified in house dust from the U.S., in marine mammals; concentrations of these compounds in dolphins and porpoises ranged from the instrumental detection limit (IDL) (<0.04) to 70 and IDL (<0.04) to 3859 ng/g lw, respectively. Levels of TBPH were comparable to ΣHBCDs in porpoise samples. The presence of these novel flame retardants in top-trophic-level marine organisms raises concern about their release into the environment and indicates the need for further monitoring of these compounds in other environmental matrices. [ABSTRACT FROM AUTHOR]

Many studies have demonstrated that persistent organic pollutants are transferred from mother to pup during lactation in phocid seals, but none have been able to determine the significance of these findings for survivorship. The aim of this study was to investigate the relationship between blubber contaminant concentrations and first-year survival in gray seal pups. A mark-recaputre framework was used to estimate survival probabilities and animals were "marked" using novel mobile phone tugs. Individual and group covariates (sex, condition, and blubber contaminants) were embedded within a live-resighting model. The most significant covariates remained condition at weaning and sex (males in poor condition had the lowest survival probability), as was found previously, but there was also evidence indicating that higher blubber contaminants additionally decreased survivorship. The models' Akaike's Information Criteria (AICs) and their associated weights, point toward the tetrapolybrominated diphenyl ether congeners (dominated by BDE-47) as being the most important group of contaminants effecting survival probability, followed by the total dichlorodiphenyltrichloroethanes (DDTs) and pentapolychlorinated biphanyl congeners. Those compounds were not the most abundant in the blubber, suggesting further studies into their toxicological effects in this species are necessary. The specific mechanisms driving the reduction in survivorship remain unknown. [ABSTRACT FROM AUTHOR]

In an earlier paper, we reported data indicating a sharp increase in hexabromocyclododecane concentrations in the blubber of 85 harbor porpoises from the UK, from about 2001 onward. That time trend was evaluated using data from 1994-2003, generated on a diastereoisomer basis using LC-MS. In this paper we report additional data for 138 animals collected during 2003-2006. ΣHBCD concentrations ranged from <10 to 11,500 μg kg-1 wet weight (up to 12,800 μg kg-1 lipid weight) and TBBP-A was not detected in any samples. The maximum ΣHBCD concentration observed in this study was about half that seen in the earlier study (21,400 μg kg-1 lipid weight) and, in both studies, the highest concentration was for an animal stranded or by caught in 2003. Investigation of time trends confirmed a statistically significant increase between 2000 and 2001 (p <0.01) and a statistically significant decrease between 2003 and 2004 (p < 0.05). Neither trend was confounded by age, sex, nutritional status, or location. Possible contributory factors to the observed decrease include the closure in 2003 of an HBCD manufacturing plant in NE England which had considerable emissions up to 2003, and two voluntary schemes intended to reduce emissions of HBCD to the environment from industry which, however, did not formally begin until 2006. [ABSTRACT FROM AUTHOR]

A sensitive and selective method utilizing high performance liquid chromatography coupled to negative atmospheric pressure chemical ionization tandem mass spectrometry (APCI-LC/MS/MS) was developed to enable analysis of selected natural persistent organohalogens accumulated in marine biota. The analytes were three methoxylated tetrabromodiphenyl ethers (6-MeO-BDE47, 2'-MeO-BDE68, and 2',6-diMeO-BDE68), a dimethoxylated tetrabromobiphenyl (2,2'-diMeO-BB80), and two halogenated methyl bipyrroles (Cl7-MBP and Br4Cl2-DBP). These products were well resolved on a 150 mm reversed-phase column with methanol as the mobile phase. The fragmentation pathways of the Cl7-MBP and Br4Cl2-DBP produced characteristic multiple reaction monitoring (MRM) transitions. Determination was performed in the MRM mode using phenoxide ion [M-Br+O]- and product Br- ions for MeO-BDE analogues, or the precursor [M-Cl+O]- to Br- ion for Br4Cl2- DBP, and to C4NCl4- ion for Cl7-MBP. The APCI-LC/MS/ MS method is acceptable for calibration of the linearity and repeatability of all products studied in the low ng/g (lipid weight) level and with similar sensitivity to the electron ionization (EI)-GC/MS method. The proposed method was applied for quantification of natural organohalogens accumulated in melon-headed whale (Peponocephala electra) blubber (N = 15) in the Asia-Pacific Ocean. The concentration was positively correlated between different groups of compounds except for 2'-MeO-BDE68. The use of the analytical method based on negative ion APCI-LC/MS/MS would provide a new way for rapid monitoring of halogenated natural products from marine biota, such as sponges or algae. [ABSTRACT FROM AUTHOR]

The elimination kinetics of polychlorinated biphenyls (PCBs) in humans is difficult to assess in observational studies, because PCB exposure is never completely abolished. In a community with high dietary PCB exposures from whale blubber, we examined two groups of children with increased body burdens from breast-feeding. Follow-up was from ages 4.5 to 7.5 years (99 subjects) and 7 to 14 years (101 subjects). The calculations were performed by the use of structural equation models, with adjustment for body weight and dietary blubber intake as the main source of postnatal exposure. As a likely result of background exposures, apparent elimination half-lives were unexpectedly long when based on results from all cohort members. Subjects with exposures above the median and in the highest quartile showed half-lives of about 3-4 years for CB-138 and 4.5-5.5 years for CB-105 and CB-118; 6.5-7.5 years for CB-156, CB-170, and CB-187; and 7-9 years for CB-153 and CB-180. The longest half-lives correspond to elimination of the parent PCB solely with a daily fat excretion rate of 1-2 g, whereas shorter half-lives assume metabolic break-down. [ABSTRACT FROM AUTHOR]

California sea lions have high levels of persistent organic pollutants (POPs) in their blubber. Animals affected by domoic acid fast and refeed during their rehabilitation. We studied the effect of decreases in total body mass (16 ± 7% of initial body mass) on blubber POP contaminant concentrations and estimated POP burdens during fasting (12 ± 5 days) in 19 California sea lions. The effect of refeeding (92 ± 8% of initial body mass) was also investigated. Significant increases in the concentration of all POPs were found over the mass loss period and decreases during mass gain. A basic mass balance model indicated that the changes did not conform to a simple concentrating and diluting pattern and a proportion of the contaminants were lost from the lipid pool During mass loss, the lower chlorinated polychlorinated biphenyl congeners, chlordanes, and hexachlorocyclohexanes were lost at a higher rate than the other contaminant classes (particularly polybrominated diphenyl ethers). During mass gain the behavior of all contaminant classes was more consistent with the dilution model. These results indicate the importance of considering the energetic context when sampling blubber for long-term contaminant monitoring and suggest an initial approach to adjust for such differences. [ABSTRACT FROM AUTHOR]

The unknown compound UBC-1 previously described as the major organobromine contamination in the blubber extract of a hooded seal (Cystophora cristata) from the Barents Sea was identified as 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE). DPTE, which is the main component of the brominated flame retardant (BFR) Bromkal 73-5 PE, was synthesized by electrophilic addition of bromine to allyl- 2,4,6-tribromophenyl ether (ATE). The chirality of DPTE was proven by gas chromatographic enantioseparation of the synthesized racemate. On the basis of GC/ECNI-MS ion chromatograms (m/z79 and 81), OPTE was the dominating organobromine compound in blubber and brain samples of hooded seals and harp seals (Phoca groenlandica) from the Barents and Greenland Seas. The concentrations of DPTE in blubber and brain were up to 470 and 340 µg/kg wet weight. Next to DPTE, the natural dibromo-trichloromonoterpene (MHC-1), the anthropogenic BDE 47 and BOE 99, as well as ATE, 3,5-dibromo-2-(2′,4′-dibromo)-phenoxyanisole (6-MeO-BDE 47), 2-bromoallyl-2,4,6- tribromophenyl ether (BATE), and 4,6-dibromo-2-(2′,4′- dibromo)-phenoxyanisole (2′-MeO-BDE 68) were present with decreasing relevance. BATE, which was detected for the first time in environmental samples, was synthesized from DPTE by E2 elimination. In brain samples of the harp seals, DPTE, ATE, and BATE were the most abundant organobromine compounds, whereas polybrominated diphenyl ethers (PBDEs) and MHC-1 were virtually absent. This indicated that DPTE, ATE, and BATE were able to penetrate the blood-brain barrier. The general co-occurrence of ATE and BATE in samples contaminated with DPTE support the hypothesis that these compounds are biotransformation products of DPTE. Anaerobic transformation studies of DPTE with super-reduced corrinoids resulted in the formation of ATE. Furthermore, 2,4,6-tribromophenol (TBP) and two other unknown minor transformation products were detected. [ABSTRACT FROM AUTHOR]

Within the U.K. Marine Mammals Stranding Program, analysis of brominated flame retardants began in 1999. Initially, the focus of attention was the brominated diphenyl ethers. Since the withdrawal of the pentamix and octamix polybrominated diphenyl ether (PBDE) formulations from the EU market prior to August 2004, two other high- volume products, hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBP-A), have been included. We report the concentrations of these compounds in the blubber of harbor porpoises (Phocoena phocoena) stranded or dying due to physical trauma in the U.K. during the period 1994-2003. Analysis was undertaken using LC/MS method on a diastereoisomer basis. Eighty-five samples were analyzed for HBCD, and 68 of these for TBBP-A. α-HBCD dominated over the other isomers and was detected in all samples analyzed at concentrations ranging from 10 to 19 200 µg kg-1 wet weight. The maximum concentration was about double that reported in earlier U.K. studies. TBBP-A was detected in only 18 samples and at much lower concentrations, from 6 to 35 µg kg-1 wet weight. Investigation of possible time trends indicated a sharp increase in HBCD concentrations from about 2001 onward, which was not confounded by age (length), sex, nutritional status, or location. This may be a result of changing patterns of use of HBCD following limitations on the production and use of two PBDE formulations within the EU and will feed ongoing risk assessment activities. [ABSTRACT FROM AUTHOR]

Minke whale (Balaenoptera acutorostrata) blubber is rich in organohalogen contaminants, mercury, and n-3 fatty acids. In the present study we show that a daily intake of 50–200 g of minke whale blubber causes an impairment of the nonspecific and specific cellular immune system in the West Greenland sledge dog (Canis familiaris). Immune reactions were measured by mitogen (PHA, Con A) and antigen (KLH) intradermal testing, and as the study used exposure levels similar to those of Inuits and polar bears (Ursus maritimus), it is reasonable to infer that Inuits and polar bears suffer from similar decreased resistance to diseases. It is speculated that food sources are depleted by thinning sea ice due to climate change and that more research should assess the forecasted rise in additive immunopathy effects in polar bears. Additionally, our study suggests that the fatty acid composition may be of importance when investigating combined immunotoxic effects of contaminated food resources in future Inuit and polar bear studies. [ABSTRACT FROM AUTHOR]