PAHs in franciscana dolphins from the Southwestern Atlantic Ocean: Concentration and maternal transfer assessments.

Polycyclic aromatic hydrocarbons (PAHs) are organic compounds ubiquitous in the environment and known for their toxic, mutagenic, and carcinogenic effects. These compounds can bioaccumulate in the biota and be transferred through trophic webs. The franciscana dolphin (Pontoporia blainvillei), as top predators, can be an environmental sentinels. Thus, this study aimed to provide data about PAHs concentration in their hepatic tissue collected on the coast of Espírito Santo (Franciscana Management Area, FMA Ia), Rio de Janeiro (FMA IIa), and São Paulo states (FMA IIb), in Southeastern Brazil. PAHs were detected in 86 % of franciscana dolphins (n = 50). The highest ∑PAHsTotal median concentration was reported in FMA Ia followed by FMA IIb and FMA IIa (1055.6; 523.9, and 72.1 ng.g-1 lipid weight, respectively). Phenanthrene was detected in one fetus and two neonates, showing maternal transfer of PAHs in these dolphins. Evaluating PAHs with potential toxic effects is of utmost importance for the conservation of a threatened species.

Dolphin leukocytes exhibit an attenuated cytokine response and increase heme oxygenase activity upon exposure to lipopolysaccharides.

Cetaceans exhibit physiological adaptations that allowed the transition to aquatic life, including a robust antioxidant defense system that prevents injury from repeated exposure to ischemia/reperfusion events associated with breath-hold diving. The signaling cascades that characterize ischemic inflammation in humans are well characterized. In contrast, cetaceans' molecular and biochemical mechanisms that confer tolerance to inflammatory events are poorly understood. Heme oxygenase (HO) is a cytoprotective protein with anti-inflammatory properties. HO catalyzes the first step in the oxidative degradation of heme. The inducible HO-1 isoform is regulated by various stimuli, including hypoxia, oxidant stress, and inflammatory cytokines. The objective of this study was to compare the response of HO-1 and cytokines to a proinflammatory challenge in leukocytes isolated from humans and bottlenose dolphins (Tursiops truncatus). We measured changes in HO activity, and abundance and expression of interleukin 1 beta (IL-1ß), interleukin 6 (IL-6), tumor necrosis factor-alpha (TNF-α), and heme oxygenase 1 (HMOX1) in leukocytes treated with lipopolysaccharide (LPS) for 24 and 48 h. HO activity increased (p < 0.05) in dolphin (48 h) but not human cells. TNF-α expression increased in human (24 h, 48 h), but not dolphin cells following LPS stimulation. LPS-induced cytokine expression was lower in dolphin than in human leukocytes, suggesting a blunted cytokine response in bottlenose dolphin leukocytes treated with LPS. Results suggest species-specific regulation of inflammatory cytokines in leukocytes treated with LPS, which may lead to differential responses to a pro-inflammatory challenge between marine and terrestrial mammals.

Subcellular metal distributions and metallothionein associations in rough-toothed dolphins (Steno bredanensis) from Southeastern Brazil.

Metals are subject to internal subcellular compartmentalization, altering their bioavailability. Thus, subcellular metal assessments are crucial in biomonitoring efforts. Metal distribution in three subcellular fractions (insoluble - ISF, thermolabile - TLF and thermostable - TSF) were determined by ICP-MS in Steno bredanensis specimens from Southeastern Brazil. Associations between metals, metallothionein (MT) and reduced glutathione (GSH) were also investigated. Differential metal-detoxification mechanisms were observed. MT detoxification was mostly noted for As, Cd, and Pb, while Cu, Cr, Hg, Ni, Se and Ti displayed lower MT-associations. Fe, Zn and Se, on the other hand, were poorly associated to MT, and mostly present in the ISF, indicating low bioavailability. This is the first report on subcellular Sn and Ti distribution in cetaceans and the first in this species in Brazil. Potential protective roles of essential metals against toxic elements are postulated. This study indicates that important biochemical detoxification information is obtained through subcellular fraction analyses in marine mammals.

Bioaccumulation of organic pollutants in Indo-Pacific humpback dolphin: A review on current knowledge and future prospects.

Indo-Pacific humpback dolphin (Sousa chinensis) are chronically exposed to organic pollutants since they inhabit shallow coastal waters that are often impacted by anthropogenic activities. The aim of this review was to evaluate existing knowledge on the occurrence of organic pollutants in Indo-Pacific humpback dolphins, identify knowledge gaps, and offer recommendations for future research directions. We discussed the trends in the bioaccumulation of organic pollutants in Indo-Pacific humpback dolphins focusing on sources, physicochemical properties, and usage patterns. Furthermore, we examined factors that influence bioaccumulation such as gender, age, dietary intake and tissue-specific distribution. Studies on bioaccumulation in Indo-Pacific humpback dolphin remain scarce, despite high concentrations above 13,000 ng/g lw we previously detected for PFOS, ∑PBDE and chlorinated paraffins. The maximum concentration of organochlorines detected was 157,000 ng/g wt. Furthermore, variations in bioaccumulation were shown to be caused by factors such as usage patterns and physicochemical properties of the pollutant. However, restrictions in sampling inhibit investigations on exposure pathway and toxicity of organic pollutants in Indo-Pacific humpback dolphin. We proposed the use of biopsy sampling, predictive bioaccumulation and toxicity modeling, and monitoring other emerging contaminants such as microplastics and pharmaceuticals for future health risk assessment on this critically endangered marine mammal species.

The role of metallothioneins, selenium and transfer to offspring in mercury detoxification in Franciscana dolphins (Pontoporia blainvillei).

The concentrations of mercury (Hg), selenium (Se) and metallothioneins (MT) were evaluated in fetuses, calves, juveniles and adults of the endangered coastal Franciscana dolphin (Pontoporia blainvillei) from Argentina. Mercury concentrations varied among analyzed tissues (liver, kidney, muscle and brain), with liver showing the higher concentrations in all specimens. An age-dependent accumulation was found in liver, kidney and brain. No significant relationship between Hg and MT concentrations was found for all tissues analyzed. Hepatic Hg molar concentrations were positively correlated with those of Se, indicating a great affinity between these two elements. Furthermore, dark granules of HgSe were observed in Kupffer cells in the liver by electron microscopy, suggesting the role of this macrophage in the detoxification of Hg. A transfer of Hg through placenta was proved. The presence of Hg in brain in all age classes did not show concentrations associated with neurotoxicity.

Mercury species, selenium, metallothioneins and glutathione in two dolphins from the southeastern Brazilian coast: Mercury detoxification and physiological differences in diving capacity.

In the present study, the concentration of trace elements, total mercury (Hg) and selenium (Se) and mercury forms (MeHg, Hginorg and HgSe) in the vulnerable coastal dolphins Pontoporia blainvillei and Sotalia guianensis were appraised and compared, using metallothioneins (MT) and glutathione (GSH) as biomarkers for trace element exposure. The trace element concentrations varied between muscle and liver tissues, with liver of all dolphin specimens showing higher Hg and Se concentrations than those found in muscle. Hg, MeHg and Hginorg molar concentrations showed a clear increase with Se molar concentrations in the liver of both dolphins, and Se concentrations were higher than those of Hg on a molar basis. Se plays a relevant role in the detoxification of MeHg in the hepatic tissue of both dolphins, forming Hg-Se amorphous crystals in liver. In contrast, MT were involved in the detoxification process of Hginorg in liver. GSH levels in P. blainvillei and S. guianensis muscle tissue suggest that these dolphins have different diving capacities. Muscle Hg concentrations were associated to this tripeptide, which protects dolphin cells against Hg stress.

The skin of Commerson's dolphins (Cephalorhynchus commersonii) as a biomonitor of mercury and selenium in Subantarctic waters.

The skin of bycaught Commerson's dolphins was tested for mercury (Hg) and selenium (Se) biomonitoring in Subantarctic environments. The correlation of levels detected in the skin with those found in internal tissues - lung, liver, kidney and muscle - was assessed to evaluate how skin represents internal Hg and Se distribution for monitoring purposes. Mercury in skin had a concentration range of 0.68-3.11 µg g(-1) dry weight (DW), while Se had a higher concentration range of 74.3-124.5 µg g(-1) DW. There was no significant correlation between selenium levels in any of the analyzed tissues. Thus, the skin selenium concentration did not reflect the tissular Se levels and did not provide information for biomonitoring. The lack of correlation is explained by the biological role of Se, provided that each tissue regulates Se levels according to physiological needs. However, the skin Hg level had significant positive correlation with the levels in internal tissues (ANOVA p<0.05), particularly with that of muscle (R(2)=0.79; ANOVA p=0.0008). Thus, this correlation permits the estimation of Hg content in muscle based on the multiplication of skin biopsy levels by a factor of 1.85. Mercury bioindication using skin biopsies is a non-lethal approach that allows screening of a large number of specimens with little disturbance and makes possible an adequate sampling strategy that produces statistically valid results in populations and study areas. The correlation between Hg levels in the skin and internal tissues supports the use of the epidermis of Commerson's dolphins for Hg biomonitoring in the waters of the Subantarctic, which is a poorly studied region regarding Hg levels, sources and processes.

Investigation of trophic level and niche partitioning of 7 cetacean species by stable isotopes, and cadmium and arsenic tissue concentrations in the western Pacific Ocean.

A total of 24 stranded or bycatch cetaceans, including Balaenoptera omurai, Lagenodelphis hosei, Kogia sima, Stenella attenuata, Grampus griseus, Neophocaena phocaenoides, and Sousa chinensis, were collected from 2001 to 2011 in Taiwan. Using the muscular δ(13)C and δ(15)N data, three ecological groups were identified as the oceanic baleen whale, the neritic, and the coastal toothed whale groups, coinciding with their taxonomy, feeding habits and geographical distribution. A horizontal inshore to offshore distribution was found for the sympatric neritic toothed dolphins, G. griseus, K. sima, S. attenuata, and L. hosei in the outermost offshore waters, accompanying their growth. For the first time we identify Taiwan's Chinese white dolphin, S. chinensis, as an exclusive fish eater. Cd and As bioaccumulated in the G. griseus, L. hosei and S. attenuata increase as they grow. Prey-derived As- and Cd-induced health threats were found in L. hosei, and G. griseus.

Blubber cortisol: a potential tool for assessing stress response in free-ranging dolphins without effects due to sampling.

When paired with dart biopsying, quantifying cortisol in blubber tissue may provide an index of relative stress levels (i.e., activation of the hypothalamus-pituitary-adrenal axis) in free-ranging cetacean populations while minimizing the effects of the act of sampling. To validate this approach, cortisol was extracted from blubber samples collected from beach-stranded and bycaught short-beaked common dolphins using a modified blubber steroid isolation technique and measured via commercially available enzyme immunoassays. The measurements exhibited appropriate quality characteristics when analyzed via a bootstraped stepwise parallelism analysis (observed/expected = 1.03, 95%CI: 99.6 - 1.08) and showed no evidence of matrix interference with increasing sample size across typical biopsy tissue masses (75-150 mg; r(2) = 0.012, p = 0.78, slope = 0.022 ng(cortisol deviation)/ul(tissue extract added)). The relationships between blubber cortisol and eight potential cofactors namely, 1) fatality type (e.g., stranded or bycaught), 2) specimen condition (state of decomposition), 3) total body length, 4) sex, 5) sexual maturity state, 6) pregnancy status, 7) lactation state, and 8) adrenal mass, were assessed using a Bayesian generalized linear model averaging technique. Fatality type was the only factor correlated with blubber cortisol, and the magnitude of the effect size was substantial: beach-stranded individuals had on average 6.1-fold higher cortisol levels than those of bycaught individuals. Because of the difference in conditions surrounding these two fatality types, we interpret this relationship as evidence that blubber cortisol is indicative of stress response. We found no evidence of seasonal variation or a relationship between cortisol and the remaining cofactors.

Comparison of mercury contamination in live and dead dolphins from a newly described species, Tursiops australis.

Globally it is estimated that up to 37% of all marine mammals are at a risk of extinction, due in particular to human impacts, including coastal pollution. Dolphins are known to be at risk from anthropogenic contaminants due to their longevity and high trophic position. While it is known that beach-cast animals are often high in contaminants, it has not been possible to determine whether levels may also be high in live animals from the same populations. In this paper we quantitatively assess mercury contamination in the two main populations of a newly described dolphin species from south eastern Australia, Tursiops australis. This species appear to be limited to coastal waters in close proximity to a major urban centre, and as such is likely to be vulnerable to anthropogenic pollution. For the first time, we were able to compare blubber mercury concentrations from biopsy samples of live individuals and necropsies of beach-cast animals and show that beach-cast animals were highly contaminated with mercury, at almost three times the levels found in live animals. Levels in live animals were also high, and are attributable to chronic low dose exposure to mercury from the dolphin's diet. Measurable levels of mercury were found in a number of important prey fish species. This illustrates the potential for low dose toxins in the environment to pass through marine food webs and potentially contribute to marine mammal deaths. This study demonstrates the potential use of blubber from biopsy samples to make inferences about the health of dolphins exposed to mercury.

Could feeding habit and migratory behaviour be the causes of different toxicological hazard to cetaceans of Gulf of California (Mexico)?

In this work, a suite of diagnostic biomarkers was applied to seven cetacean species to evaluate the role of the feeding habits and migratory behavior in the toxicological status of these species from the Gulf of California, Mexico. We investigate the interspecific differences in cytochrome P450 1A1 and 2B (CYP1A1 and CYP2B, respectively), aryl hydrocarbon receptor and E2F transcription factor 1 and the contaminants levels [organochlorine compounds, polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs)] in four odontocete species (common bottlenose dolphin, long-beaked common dolphin, sperm whale and killer whale) and three mysticete species (blue whale, fin whale, and Bryde's whale) using skin biopsy. Differences in contaminant levels and molecular biomarker responses between the odontocete and mysticete species have been pointed out. The canonical discriminant analysis on principal component analysis factors, performed to reveal clustering variables, shows that odontocete are characterised by the highest levels of lipophilic contaminants compared to the mysticete, with the highest levels of polychlorinated biphenyls, dichlorodiphenyltrichloroethanes and PBDEs detected in killer whale and the lowest levels in Bryde's whale. The biomarker data show interspecific differences amongst the seven species, revealing highest CYP1A and CYP2B protein levels in the mysticete fish-eating species (Bryde's whale). In conclusion, three main factors seem to regulate the biomarker responses in these species: (a) the inductive ability of persistent organic pollutants and PAHs; (b) the different evolutionary process of the two CYPs related to the different feeding habits of the species; (c) the migratory/resident behaviour of the mysticete species in this area.

Hemoglobin as a major binding protein for methylmercury in white-sided dolphin liver.

As methylmercury (MeHg) can be bioaccumulated and biomagnified in the trophic web, its toxicity for marine mammals is of major concern. Mercury speciation in marine biota has been widely studied, mainly focused on the discrimination and quantification of inorganic Hg and MeHg. Less attention has been paid to the interactions of Hg with biomolecules and the characterization of its specific binding, which play a key role in metabolic pathways controlling its uptake, transformation, and toxicity. In the studied white-sided dolphin (Lagenorhynchus acutus) liver homogenate (QC04LH4) sample, approximately 60% of the total MeHg was found in the water soluble fraction, specifically associated with high molecular weight biomolecules. The identity of the involved proteins was investigated (after tryptic digestion of the fraction) by µRPLC with parallel detection by ICP-MS and ESI-MS/MS. Molecular mass spectrometry experiments were carried out at high resolution (100000) to ensure accurate protein identification and determination of the MeHg binding sites. Cysteine residue on the dolphin hemoglobin ß chain was found to be the main MeHg binding site, suggesting that hemoglobin is a major MeHg binding protein in this marine mammal and could be a potential carrier of this MeHg from blood to liver prior to its degradation in this organ. In parallel, a significant proportion of selenium was found to be present as selenoneine and a potential role for this compound in Hg detoxification is discussed.

Compositional discrimination of decompression and decomposition gas bubbles in bycaught seals and dolphins.

Gas bubbles in marine mammals entangled and drowned in gillnets have been previously described by computed tomography, gross examination and histopathology. The absence of bacteria or autolytic changes in the tissues of those animals suggested that the gas was produced peri- or post-mortem by a fast decompression, probably by quickly hauling animals entangled in the net at depth to the surface. Gas composition analysis and gas scoring are two new diagnostic tools available to distinguish gas embolisms from putrefaction gases. With this goal, these methods have been successfully applied to pathological studies of marine mammals. In this study, we characterized the flux and composition of the gas bubbles from bycaught marine mammals in anchored sink gillnets and bottom otter trawls. We compared these data with marine mammals stranded on Cape Cod, MA, USA. Fresh animals or with moderate decomposition (decomposition scores of 2 and 3) were prioritized. Results showed that bycaught animals presented with significantly higher gas scores than stranded animals. Gas composition analyses indicate that gas was formed by decompression, confirming the decompression hypothesis.

Anthropogenic contaminants in Indo-Pacific humpback and Australian snubfin dolphins from the central and southern Great Barrier Reef.

We present the first evidence of accumulation of organochlorine compounds (DDTs, PCBs, HCB) and polycyclic aromatic hydrocarbons (PAHs) in Indo-Pacific humpback and Australian snubfin dolphins from the central and southern Great Barrier Reef. These dolphins are considered by the Great Barrier Marine Park Authority to be high priority species for management. Analyses of biopsy samples, collected from free ranging individuals, showed PAHs levels comparable to those reported from highly industrialized countries. DDTs and HCB were found at low levels, while in some individuals, PCBs were above thresholds over which immunosuppression and reproductive anomalies occur. These results highlight the need for ongoing monitoring of these and other contaminants, and their potential adverse effects on dolphins and other marine fauna. This is particularly important given the current strategic assessment of the Great Barrier Reef World Heritage Area being undertaken by the Australian Government and the Queensland Government.

Validation of blubber progesterone concentrations for pregnancy determination in three dolphin species and a porpoise.

Recent studies have validated the use of biopsies as a minimally invasive way to identify pregnant females in several species of wild cetaceans: Balaenapteraacutorostrata , Delphinusdelphis , Lissodelphisborealis, and Lagenorhynchusobliquidens. These studies found that progesterone (P4) concentrations quantified from blubber attached to biopsy samples is diagnostic of pregnancy. Here we examine a broader group of cetacean species in efforts to investigate how progesterone levels vary between species with respect to pregnancy status. We compared P4 concentrations in blubber collected from fishery bycatch and beach-stranded specimens for 40 females of known reproductive condition from Delphinuscapensis (n = 18), Stenellaattenuata (n = 8), S. longirostris (n = 6), and Phocoenoidesdalli (n = 8). The P4 concentrations were different (t = -7.1, p = 1.79E-08) between pregnant and non-pregnant animals in all species, with the mean blubber P4 concentration for pregnant animals 164 times higher than that of non-pregnant animals. There was no overlap in concentration levels between sexually immature or non-pregnant sexually mature animals and pregnant animals. No significant differences (F = 0.354, p = 0.559) were found between mature non-pregnant and immature D. capensis and Pdalli, suggesting P4 level is not indicative of maturity state in female delphinoids. P4 concentrations in relation to reproductive state were remarkably similar across species. All samples were analyzed with two different enzyme immunoassay kits to gauge assay sensitivity to measure progesterone in small samples, such as biopsies. With the technique now validated for these cetacean species, blubber P4 is a reliable diagnostic of pregnancies across multiple species, and thus expands the utility of this method to study reproduction in free-ranging cetaceans using biopsies.

Fine scale distribution constrains cadmium accumulation rates in two geographical groups of Franciscana dolphin from Argentina.

Franciscana dolphin is an endemic cetacean in the southwestern Atlantic Ocean and is classified as Vulnerable A3d by the International Union for Conservation of Nature. Cadmium accumulation was assessed in two geographic groups from Argentina; one inhabits the La Plata River estuary, a high anthropogenic impacted environment, and the other is distributed in marine coastal, with negligible pollution. Despite the environment, marine dolphins showed an increase of renal Cd concentrations since trophic independence; while in estuarine dolphins was from 6 years. This is associated with dietary Argentine anchovy which was absent in the diet of estuarine dolphins, being a trophic vector of cadmium in shelf waters of Argentina. Cluster analysis also showed high levels of cd in association with the presence of anchovy in the stomach. The difference in the fine scale distribution of species influences dietary exposure to Cd and, along with other data, indicates two stocks in Argentina.

Nontargeted comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry method and software for inventorying persistent and bioaccumulative contaminants in marine environments.

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.

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are major contributors to the persistent organobromine load in sub-Arctic and Arctic marine mammals, 1986-2009.

A selection of MeO-BDE and BDE congeners were analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography. The analysis was performed using both low resolution and high resolution GC-MS. MeO-PBDE concentrations relative to total PBDE concentrations varied greatly between sampling periods and species. The highest MeO-PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, often exceeding the concentration of the most abundant PBDE, BDE-47. The lowest MeO-PBDE levels were found in fin whales and ringed seals. The main MeO-BDE congeners were 6-MeO-BDE47 and 2'-MeO-BDE68. A weak correlation only between BDE47 and its methoxylated analog 6-MeO-BDE47 was found and is indicative of a natural source for MeO-PBDEs.

Increasing levels of long-chain perfluorocarboxylic acids (PFCAs) in Arctic and North Atlantic marine mammals, 1984-2009.

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hisida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.

Polybrominated diphenyl ethers (PBDEs) in marine mammals from Arctic and North Atlantic regions, 1986-2009.

A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments.