Comparison of δ13C and δ15N of ecologically relevant amino acids among beluga whale tissues.

Ecological applications of compound-specific stable isotope analysis (CSIA) of amino acids (AAs) include 1) tracking carbon pathways in food webs using essential AA (AAESS) δ13C values, and 2) estimating consumer trophic position (TP) by comparing relative differences of 'trophic' and 'source' AA δ15N values. Despite the significance of these applications, few studies have examined AA-specific SI patterns among tissues with different AA compositions and metabolism/turnover rates, which could cause differential drawdown of body AA pools and impart tissue-specific isotopic fractionation. To address this knowledge gap, especially in the absence of controlled diet studies examining this issue in captive marine mammals, we used a paired-sample design to compare δ13C and δ15N values of 11 AAs in commonly sampled tissues (skin, muscle, and dentine) from wild beluga whales (Delphinapterus leucas). δ13C of two AAs, glutamic acid/glutamine (Glx, a non-essential AA) and, notably, threonine (an essential AA), differed between skin and muscle. Furthermore, δ15N of three AAs (alanine, glycine, and proline) differed significantly among the three tissues, with glycine δ15N differences of approximately 10 ‰ among tissues supporting recent findings it is unsuitable as a source AA. Significant δ15N differences in AAs such as proline, a trophic AA used as an alternative to Glx in TP estimation, highlight tissue selection as a potential source of error in ecological applications of CSIA-AA. Amino acids that differed among tissues play key roles in metabolic pathways (e.g., ketogenic and gluconeogenic AAs), pointing to potential physiological applications of CSIA-AA in studies of free-ranging animals. These findings underscore the complexity of isotopic dynamics within tissues and emphasize the need for a nuanced approach when applying CSIA-AA in ecological research.

Mixture effect assessment applying in vitro bioassays to in-tissue silicone extracts of traditional foods prepared from beluga whale blubber.

We complement an earlier study on the nutrient and environmental contaminant levels in Arctic beluga whale traditional foods by mixture effect assessment using in vitro bioassays. Mixtures were extracted by in-tissue sampling of raw blubber and several traditional food preparations including Muktuk and Uqsuq using silicone (polydimethylsiloxane, PDMS) as sampler. PDMS extracts persistent and degradable neutral organic chemicals of a wide range of hydrophobicity with defined lipid-PDMS partition ratios. The solvent extracts of PDMS were dosed in various reporter gene assays based on human cell lines. Cytotoxicity was consistent across all cell lines and was a good indicator of overall chemical burden. No hormone-like effects on the estrogen receptor, the progesterone receptor and the glucocorticoid receptor were observed but a few samples activated the androgen receptor, albeit with low potency. The peroxisome-proliferator activated receptor (PPARγ) was the most sensitive endpoint followed by activation of oxidative stress response and activation of the arylhydrocarbon (AhR) receptor. The detected pollutants only explained a small fraction of the experimental mixture effects, indicating additional bioactive pollutants. The effect levels of the extracted mixtures were higher than those observed in blubber extracts of dugongs living off the shore of Australia. Roasting over an open fire or food preparation near a smokehouse led to increased PAH levels that were reflected in increased oxidative stress response and activation of the AhR. So far in vitro assays have only been used to quantify persistent dioxin-like chemicals in food and feed but this pilot study demonstrates a much broader potential for food safety evaluations complementing chemical analytical monitoring.

Reference intervals and values for fecal cortisol, aldosterone, and the ratio of cortisol to dehydroepiandrosterone metabolites in four species of cetaceans.

The goal of the current study was to create reference intervals and values for several common and one potential novel physiological indicators of animal welfare for four species of cetaceans. The subjects included 189 bottlenose dolphins (Tursiops truncatus), 27 Indo-Pacific bottlenose dolphins (Tursiops aduncus), eight Pacific white-sided dolphins (Lagenorhynchus obliquidens), and 13 beluga whales (Delphinapterus leucas) at Alliance of Marine Mammal Parks and Aquariums and/or Association of Zoos and Aquariums accredited facilities. During two sampling time periods between July and November of 2018 and between January and April of 2019, fecal samples were collected weekly for five weeks from all animals. Samples were processed and analyzed using enzyme immunoassay for fecal cortisol, aldosterone, and dehydroepiandrosterone (DHEA) metabolites. Linear mixed models were used to examine demographic and time factors impacting hormone metabolite concentrations. Age, sex, and time of year were all significant predictors for some of the models (p < 0.01). An iOS mobile application ZooPhysioTrak was created for easy access to species-specific reference intervals and values accounting for significant predictors. For facilities without access to this application, additional reference intervals and values were constructed without accounting for significant predictors. Information gained from this study and the use of the application can provide reference intervals and values to make informed management decisions for cetaceans in zoological facilities.

A comparative analysis of cone photoreceptor morphology in bowhead and beluga whales.

The cetacean visual system is a product of selection pressures favoring underwater vision, yet relatively little is known about it across taxa. Previous studies report several mutations in the opsin genetic sequence in cetaceans, suggesting the evolutionary complete or partial loss of retinal cone photoreceptor function in mysticete and odontocete lineages, respectively. Despite this, limited anatomical evidence suggests cone structures are partially maintained but with absent outer and inner segments in the bowhead retina. The functional consequence and anatomical distributions associated with these unique cone morphologies remain unclear. The current study further investigates the morphology and distribution of cone photoreceptors in the bowhead whale and beluga retina and evaluates the potential functional capacity of these cells' alternative to photoreception. Refined histological and advanced microscopic techniques revealed two additional cone morphologies in the bowhead and beluga retina that have not been previously described. Two proteins involved in magnetosensation were present in these cone structures suggesting the possibility for an alternative functional role in responding to changes in geomagnetic fields. These findings highlight a revised understanding of the unique evolution of cone and gross retinal anatomy in cetaceans, and provide prefatory evidence of potential functional reassignment of these cells.

Associations between organohalogen exposure and thyroid- and steroid-related gene responses in St. Lawrence Estuary belugas and minke whales.

Elevated concentrations of persistent organic pollutants (POPs) and emerging halogenated flame retardants (HFRs) have been reported in tissues of the endangered St. Lawrence Estuary (Canada) beluga population as well as in minke whales visiting that same feeding area. This study examined the linkages between blubber concentrations of POPs and emerging HFRs, and transcription in skin of genes involved in the regulation of thyroid and steroid axes in belugas and minke whales from the St. Lawrence Estuary. In belugas, concentrations of PCBs, OCs and hexabromobenzene (HBB) were positively correlated with the transcription of thyroid- and/or steroid-related genes, while Dec-604 CB concentrations were negatively associated with the transcription of glucocorticoid and thyroid genes. In minke whales, PBDE concentrations changed positively with Esrß transcript levels and HBB concentrations negatively with Nr3c1 transcripts. Present results suggest that several biological functions including reproduction and energetic metabolism may represent potential targets for organohalogens in these whales.

Papillomatous Skin Netting of Cetaceans (Cetacea: Delphinapterus leucas, Balaena mysticetus, and Eschrichtius robustus) and Sirens (Sirenia: Trichechus manatus and Dugong dugon).

The structure of the papillomatous junction between epidermis and dermis (papillomatous netting, PN) in the skin of cetaceans (white whales, bowhead, and gray whales) and sirens (American manatee, dugong) was studied and compared using histophysiological and morphogeometric methods. The relative extent of PN development proved to be similar in members of both orders, but significant differences were found in PN configuration, the volume of "free area of grille", the degree of skin vertical compression, and skin density, which influence buoyancy. The differences are discussed from the viewpoint of species biology.

Temporal trends of PBDEs and emerging flame retardants in belugas from the St. Lawrence Estuary (Canada) and comparisons with minke whales and Canadian Arctic belugas.

An exponential level increase of the ubiquitous halogenated flame retardant (HFR) class polybrominated diphenyl ether (PBDE) has been documented during the 1990s in endangered belugas (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Eastern Canada. The recent worldwide bans and regulations of PBDE mixtures led to their replacement by alternative HFRs (so-called emerging HFRs) that are increasingly being reported in various environmental compartments. There are, however, limited knowledge on the spatial and temporal trends of PBDEs and emerging HFRs in cetaceans, especially after restrictions on PBDE usage. The first objective of this study was to investigate the occurrence of HFRs (35 PBDE congeners and 13 emerging compounds) in the blubber of belugas and minke whales (Balænoptera acutorostrata) found dead in the Estuary or Gulf of St. Lawrence as well as belugas from Nunavik (Canadian Arctic) collected as part of the Inuit subsistence hunt. A second objective was to investigate the trends of HFR concentrations in SLE beluga males between 1997 and 2013. PBDEs were the most abundant HFRs in all three whale populations, while hexabromobenzene (HBB), Chlordene Plus (CPlus), Dechlorane Plus (DP), and Dechlorane 604 Component B (Dec-604 CB) were quantified in the majority of blubber samples. Overall, concentrations of emerging HFRs were notably greater in SLE belugas compared to the two other whale populations, with the exception of DP and Dec-604 CB that were found in greater concentrations in Canadian Arctic belugas. No significant trend in blubber PBDE concentrations was found in SLE belugas during this 17-year period. This suggests that global PBDE regulations are too recent to observe changes in PBDE concentrations in belugas from this highly HFR-exposed environment. In contrast, concentrations of HBB and CPlus in SLE belugas decreased slightly from 1997 to 2013, while DP increased up until 2000 and decreased slightly thereafter. The occurrence and temporal variations of PBDEs and their replacement products in these cetaceans warrant continuous monitoring.

Circulating thyroid hormones and associated metabolites in white whales (Delphinapterus leucas) determined using isotope-dilution mass spectrometry.

Blood was sampled from nine free-ranging white whales (beluga whale, Delphinapterus leucas) from Svalbard, Norway during the summers of 2013 and 2014. Total concentrations of eleven thyroid hormones and metabolites were measured in serum using a novel liquid chromatography tandem mass spectrometry analytical method. Measurements of these compounds in plasma gave the same results as in serum. The three hormones found in highest concentrations were 3,3',5-triiodothyronine (T3), 3,3',5'-triiodothyronine (rT3) and thyroxine (T4). Traces of associated metabolites were also found.

Testosterone and progesterone concentrations in blow samples are biologically relevant in belugas (Delphinapterus leucas).

Steroid hormone analysis in blow (respiratory vapor) may provide a minimally invasive way to assess the reproductive status of wild cetaceans. Biological validation of the method is needed to allow for the interpretation of hormone measurements in blow samples. Utilizing samples collected from trained belugas (Delphinapterus leucas, n=20), enzyme immunoassays for testosterone and progesterone were validated for use with beluga blow samples. Testosterone concentrations in 40 matched blood and blow samples collected from 4 male belugas demonstrated a positive correlation (R2=0.52, p<0.0001). Progesterone concentrations in 64 matching blood and blow samples from 11 females were also positively correlated (R2=0.60, p<0.0001). Testosterone concentrations (mean±SD) in blow samples collected from adult males (119.3±14.2pg/ml) were higher (p<0.01) than that of a juvenile male (<8years) (59.4±6.5pg/ml) or female belugas (54.1±25.7pg/ml). Among adult males, testosterone concentrations in blow demonstrated a seasonal pattern of secretion, with peak secretion occurring during the breeding season (February-April, 136.95±33.8pg/ml). Progesterone concentrations in blow varied by reproductive status; pregnant females (410.6±87.8pg/ml) and females in the luteal phase of the estrous cycle (339.5±51.0pg/ml) had higher (p<0.0001) blow progesterone concentrations than non-pregnant females without a corpus luteum (242.5±27.3pg/ml). Results indicate that blow sample analysis can be used to detect variation in reproductive states associated with large differences in circulating testosterone or progesterone in belugas.

Natural Hg isotopic composition of different Hg compounds in mammal tissues as a proxy for in vivo breakdown of toxic methylmercury.

In the last decade, specific attention has been paid to total mercury (HgT) stable isotopic composition, especially in natural samples such as aquatic organisms, due to its potential to track the cycle of this toxic element in the environment. Here, we investigated Hg Compound Specific stable Isotopic Composition (CSIC) of natural inorganic Hg (iHg) and methylmercury (MMHg) in various tissues of aquatic mammals (Beluga whale from the Arctic marine environment and seals from the freshwater lake Baikal, Russia). In seals' organs the variation in mass dependent fractionation (MDF, δ(202)Hg) for total Hg was significantly correlated to the respective fraction of iHg and MMHg compounds, with MMHg being enriched by ∼ 3‰ in heavier isotopes relative to iHg. On the other hand, we observe insignificant variation in Hg mass independent isotope fractionation (MIF, Δ(199)Hg) among iHg and MMHg in all organs for the same mammal species and MMHg in prey items. MIF signatures suggest that both MMHg and iHg in aquatic mammals have the same origin (i.e., MMHg from food), and are representative of Hg photochemistry in the water column of the mammal ecosystem. MDF signatures of Hg compounds indicate that MMHg is demethylated in vivo before being stored in the muscle, and the iHg formed is stored in the liver, and to a lesser extent in the kidney, before excretion. Thus, Hg CSIC analysis in mammals can be a powerful tool for tracing the metabolic response to Hg exposure.

Lactational Transfer of Polychlorinated-Biphenyls (PCBs) and Other Organochlorines in St. Lawrence Beluga Whales (Delphinapterus leucas).

This study uses an individual-based contaminant bioaccumulation model for marine mammals to explore factors controlling the transfer of PCBs from mother to calf via nursing in beluga from the St. Lawrence Estuary. Beluga blubber samples (n = 46), along with four matched milk samples from stranded animals over the 1986-1994 period were used for comparison with modelled results. Based on 68 POPs, including 48 PCBs and 20 other organochlorine compounds, milk:blubber ratios were 0.65 between log K OW 3-6.5, then decreased to 0.1 at log K OW 8. Model simulations based on this relationship indicated females were transferring PCBs that were relatively very hydrophobic and highly chlorinated less readily than their lower chlorinated counterparts, resulting in an enriched concentration of very hydrophobic congeners in nursing females relative to adult males. There was very good agreement between observed and modelled male:female PCB concentration ratios. Four females within our dataset (15 %) had male-like ΣPCB concentrations as well as male-like congener profiles, suggesting that these individuals may have had a reduced or limited nursing history.

Distant drivers or local signals: where do mercury trends in western Arctic belugas originate?

Temporal trends of contaminants are monitored in Arctic higher trophic level species to inform us on the fate, transport and risk of contaminants as well as advise on global emissions. However, monitoring mercury (Hg) trends in species such as belugas challenge us, as their tissue concentrations reflect complex interactions among Hg deposition and methylation, whale physiology, dietary exposure and foraging patterns. The Beaufort Sea beluga population showed significant increases in Hg during the 1990 s; since that time an additional 10 years of data have been collected. During this time of data collection, changes in the Arctic have affected many processes that underlie the Hg cycle. Here, we examine Hg in beluga tissues and investigate factors that could contribute to the observed trends after removing the effect of age and size on Hg concentrations and dietary factors. Finally, we examine available indicators of climate variability (Arctic Oscillation (AO), the Pacific Decadal Oscillation (PDO) and sea-ice minimum (SIM) concentration) to evaluate their potential to explain beluga Hg trends. Results reveal a decline in Hg concentrations from 2002 to 2012 in the liver of older whales and the muscle of large whales. The temporal increases in Hg in the 1990 s followed by recent declines do not follow trends in Hg emission, and are not easily explained by diet markers highlighting the complexity of feeding, food web dynamics and Hg uptake. Among the regional-scale climate variables the PDO exhibited the most significant relationship with beluga Hg at an eight year lag time. This distant signal points us to consider beluga winter feeding areas. Given that changes in climate will impact ecosystems; it is plausible that these climate variables are important in explaining beluga Hg trends. Such relationships require further investigation of the multiple connections between climate variables and beluga Hg.

Blow collection as a non-invasive method for measuring cortisol in the beluga (Delphinapterus leucas).

Non-invasive sampling techniques are increasingly being used to monitor glucocorticoids, such as cortisol, as indicators of stressor load and fitness in zoo and wildlife conservation, research and medicine. For cetaceans, exhaled breath condensate (blow) provides a unique sampling matrix for such purposes. The purpose of this work was to develop an appropriate collection methodology and validate the use of a commercially available EIA for measuring cortisol in blow samples collected from belugas (Delphinapterus leucas). Nitex membrane stretched over a petri dish provided the optimal method for collecting blow. A commercially available cortisol EIA for measuring human cortisol (detection limit 35 pg ml-1) was adapted and validated for beluga cortisol using tests of parallelism, accuracy and recovery. Blow samples were collected from aquarium belugas during monthly health checks and during out of water examination, as well as from wild belugas. Two aquarium belugas showed increased blow cortisol between baseline samples and 30 minutes out of water (Baseline, 0.21 and 0.04 µg dl-1; 30 minutes, 0.95 and 0.14 µg dl-1). Six wild belugas also showed increases in blow cortisol between pre and post 1.5 hour examination (Pre 0.03, 0.23, 0.13, 0.19, 0.13, 0.04 µg dl-1, Post 0.60, 0.31, 0.36, 0.24, 0.14, 0.16 µg dl-1). Though this methodology needs further investigation, this study suggests that blow sampling is a good candidate for non-invasive monitoring of cortisol in belugas. It can be collected from both wild and aquarium animals efficiently for the purposes of health monitoring and research, and may ultimately be useful in obtaining data on wild populations, including endangered species, which are difficult to handle directly.

Molecular and neurochemical biomarkers in Arctic beluga whales (Delphinapterus leucas) were correlated to brain mercury and selenium concentrations.

Mercury (Hg) concentrations have increased in western Arctic beluga whales (Delphinapterus leucas) since the industrial revolution. Methylmercruy (MeHg) is a known neurotoxicant, yet little is known about the risk of exposure for beluga whales. Selenium (Se) has been linked to demethylation of MeHg in cetaceans, but its role in attenuating Hg toxicity in beluga whales is poorly understood. The objective of this study is to explore relationships between Hg and Se concentrations and neurochemical biomarkers in different brain regions of beluga whales in order to assess potential neurotoxicological risk of Hg exposure in this population. Brain tissue was sampled from hunter-harvested beluga whales from the western Canadian Arctic in 2008 and 2010. Neurochemical and molecular biomarkers were measured with radioligand binding assays and quantitative PCR, respectively. Total Hg (HgT) concentration ranged from 2.6-113 mg kg(-1) dw in temporal cortex. Gamma-amminobutyric acid type A receptor (GABAA-R) binding in the cerebellum was negatively associated with HgT, MeHg and total Se (SeT) concentrations (p ≤ 0.05). The expression of mRNA for GABAA-R subunit α2 was negatively associated with HgT and MeHg (p ≤ 0.05). Furthermore, GABAA-R binding was positively correlated to mRNA expression for GABAA-R α2 subunit, and negatively correlated to the expression of mRNA for GABAA-R α4 subunit (p ≤ 0.05). The expression of N-methyl-d-aspartate receptor (NMDA-R) subunit 2b mRNA expression was negatively associated with iHglabile concentration in the cerebellum (p ≤ 0.05). Variation of molecular and/or biochemical components of the GABAergic and glutamatergic signaling pathways were associated with MeHg exposure in beluga whales. Our results show that MeHg exposure is associated with neurochemical variation in the cerebellum of beluga whales and Se may partially protect from MeHg-associated neurotoxicity.

Comparative hepatic in vitro depletion and metabolite formation of major perfluorooctane sulfonate precursors in Arctic polar bear, beluga whale, and ringed seal.

Perfluorooctane sulfonate (PFOS) has been reported to be among the most concentrated persistent organic pollutants in Arctic marine wildlife. The present study examined the in vitro depletion of major PFOS precursors, N-ethyl-perfluorooctane sulfonamide (N-EtFOSA) and perfluorooctane sulfonamide (FOSA), as well as metabolite formation using an assay based on enzymatically viable liver microsomes for three top Arctic marine mammalian predators, polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas), and ringed seal (Pusa hispida), and in laboratory rat (Rattus rattus) serving as a general mammalian model and positive control. Rat assays showed that N-EtFOSA (38 nM or 150 ng mL(-1)) to FOSA metabolism was >90% complete after 10 min, and at a rate of 23 pmol min(-1) mg(-1) protein. Examining all species in a full 90 min incubation assay, there was >95% N-EtFOSA depletion for the rat active control and polar bear microsomes, ∼65% for ringed seals, and negligible depletion of N-EtFOSA for beluga whale. Concomitantly, the corresponding in vitro formation of FOSA from N-EtFOSA was also quantitatively rat≈polar bear>ringed seal>>>beluga whale. A lack of enzymatic ability and/or a rate too slow to be detected likely explains the lack of N-EtFOSA to FOSA transformation for beluga whale. In the same assays, the depletion of the FOSA metabolite was insignificant (p>0.01) and with no concomitant formation of PFOS metabolite. This suggests that, in part, a source of FOSA is the biotransformation of accumulated N-EtFOSA in free-ranging Arctic ringed seal and polar bear.

A twenty-one year temporal trend of persistent organic pollutants in St. Lawrence Estuary beluga, Canada.

Persistent organic pollutants (POPs) were measured in blubber from 144 stranded adult belugas (Delphinapterus leucas) found on the shores of the St. Lawrence Estuary (SLE) between 1987 and 2007. Temporal trends of POP concentrations (ln transformed) in beluga were described by three models, zero slope (ZS), linear (L) and two-segment piecewise (PW). Often two but sometimes all three models were equivalent in describing temporal trends based on Akaike's Information Criterion for small sample sizes. Over this 21-year time period, concentrations of most legacy POPs, including PCBs, DDTs and HCHs, exhibited relatively weak (≤11% per year) but significant decreasing trends in beluga. For PBDEs, temporal trends were best described by a PW model, characterizing a rapid increase until 1997-1998 followed by a slower increase for males and a steady-state for females. Potential cofactors such as blubber lipid content and carcass state of preservation did not show any significant temporal trends over the time period considered. Nitrogen stable isotope ratios (δ(15)N) in beluga liver, a proxy of trophic level, could not be associated to any effect on temporal trends of POP concentrations in beluga. Several POPs exhibited significant relationships with age of beluga and data were age-adjusted. Temporal trends of POP concentrations adjusted for age of beluga were reassessed but results were essentially identical as those obtained with the original POP data. Overall, POP temporal trends observed in SLE beluga are consistent with changes expected from regulations and restrictions in the use of these compounds in developed countries.

Discovery and widespread occurrence of polyhalogenated 1,1'-dimethyl-2,2'-bipyrroles (PDBPs) in marine biota.

Polyhalogenated 1,1'-dimethyl-2,2'-bipyrroles (PDBPs) are halogenated natural products (HNPs) previously shown to bioaccumulate in marine mammals and birds. Since their discovery in 1999, six hexahalogenated and a few lesser halogenated congeners have been identified in diverse marine mammal samples. Here we report the identification of 17 additional hexahalogenated PDBPs in the blubber extract of a humpback dolphin (Sousa chinensis) from Queensland, Australia. Thirteen of these new PDBPs were also detected in an Australian sea cucumber (Holothuria sp.). Additional samples were also tested positive on several new PDBPs, including an Australian venus tuskfish (Choerodon venustus) as well as a white whale (Delphinapterus leucas) and a sperm whale (Physeter macrocephalus) from the Northern Hemisphere. GC/ECNI-MS-SIM quantification of the molecular ions was carried out with the help of synthesized standards. The sum concentration of PDBPs was 1.1 mg/kg lipid in the humpback dolphin and 0.48 mg/kg lipid in the sea cucumber.

Mercury distribution and speciation in different brain regions of beluga whales (Delphinapterus leucas).

The toxicokinetics of mercury (Hg) in key species of Arctic ecosystem are poorly understood. We sampled five brain regions (frontal lobe, temporal lobe, cerebellum, brain stem and spinal cord) from beluga whales (Delphinapterus leucas) harvested in 2006, 2008, and 2010 from the eastern Beaufort Sea, Canada, and measured total Hg (HgT) and total selenium (SeT) by inductively coupled plasma mass spectrometry (ICP-MS), mercury analyzer or cold vapor atomic absorption spectrometry, and the chemical forms using a high performance liquid chromatography ICP-MS. At least 14% of the beluga whales had HgT concentrations higher than the levels of observable adverse effect (6.0 mg kg(-1) wet weight (ww)) in primates. The concentrations of HgT differed between brain regions; median concentrations (mgkg(-1) ww) were 2.34 (0.06 to 22.6, 81) (range, n) in temporal lobe, 1.84 (0.12 to 21.9, 77) in frontal lobe, 1.84 (0.05 to 16.9, 83) in cerebellum, 1.25 (0.02 to 11.1, 77) in spinal cord and 1.32 (0.13 to 15.2, 39) in brain stem. Total Hg concentrations in the cerebellum increased with age (p<0.05). Between 35 and 45% of HgT was water-soluble, of which, 32 to 41% was methyl mercury (MeHg) and 59 to 68% was labile inorganic Hg. The concentration of MeHg (range: 0.03 to 1.05 mg kg(-1) ww) was positively associated with HgT concentration, and the percent MeHg (4 to 109%) decreased exponentially with increasing HgT concentration in the spinal cord, cerebellum, frontal lobe and temporal lobe. There was a positive association between SeT and HgT in all brain regions (p<0.05) suggesting that Se may play a role in the detoxification of Hg in the brain. The concentration of HgT in the cerebellum was significantly associated with HgT in other organs. Therefore, HgT concentrations in organs that are frequently sampled in bio-monitoring studies could be used to estimate HgT concentrations in the cerebellum, which is the target organ of MeHg toxicity.

Metabolic transformation shapes polychlorinated biphenyl and polybrominated diphenyl ether patterns in beluga whales (Delphinapterus leucas).

While the accumulation of persistent contaminants in marine mammals can be attributed directly to their prey, the role of metabolism in shaping patterns is often overlooked. In the present study, the authors investigated the role of metabolic transformation in influencing polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) patterns in offshore and nearshore groups of beluga whales (Delphinapterus leucas) and their prey. Congener profiles and principal components analysis (PCA) revealed similar PCB and PBDE patterns in beluga whales feeding either offshore or nearshore, despite divergent contaminant patterns in the putative prey of these two feeding groups. The clustering of PCBs into metabolically derived structure-activity groups (SAGs) and the separation of metabolizable and recalcitrant groups along principal component 1 of the PCA revealed the important role of metabolic transformation in shaping PCB patterns in beluga. Lack of metabolism for congeners with high ortho-chlorine content was revealed by metabolic slopes equal to or greater than 1.0. Metabolic slopes for all other SAGs were less than 1.0 (p<0.001), suggesting metabolism of congeners with ortho-meta and meta-para vicinal hydrogens via induction of cytochrome P450 enzymes (CYP1A/2B/3A). Metabolic indices less than 1.0 for PBDEs (p<0.001) suggested that beluga metabolized these poorly understood flame retardants. The strikingly similar PCB patterns in a captive beluga and free-ranging beluga from the Beaufort Sea provide additional evidence that metabolic transformation is a dominant driver of contaminant patterns in beluga.

Transplacental transfer of polychlorinated biphenyls and polybrominated diphenyl ethers in arctic beluga whales (Delphinapterus leucas).

This study found that arctic beluga whales (Delphinapterus leucas) transferred, on average, 11.4% (7.5 mg) and 11.1% (0.1 mg) of their polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) blubber burden to their near-term fetuses. A single physicochemical parameter, log K(OW), largely explained this transplacental transfer for PCBs (r(2) =0.79, p < 0.00001) and PBDEs (r(2) = 0.37, p = 0.007), with congeners having a log K(OW) < 6.5 preferentially transferred to the fetus. Blubber concentrations of 257 ng/g lipid weight (lw) PCBs and 3.8 ng/g (lw) PBDEs in beluga fetuses highlights the exposure to endocrine-disrupting compounds during a critical developmental stage. The implications of detecting these levels of legacy PCBs and the flame retardant PBDEs in unborn arctic beluga are unclear.