Polychlorinated Biphenyl-Related Alterations of the Expression of Essential Genes in Harbour Seals (Phoca vitulina) from Coastal Sites in Canada and the United States.

As long-lived marine mammals found throughout the temperate coastal waters of the North Pacific and Atlantic Oceans, harbour seals (Phoca vitulina) have become an invaluable sentinel of food-web contamination. Their relatively high trophic position predisposes harbour seals to the accumulation of harmful levels of persistent organic pollutants (POPs). We obtained skin/blubber biopsy samples from live-captured young harbour seals from various sites in the northeastern Pacific (British Columbia, Canada, and Washington State, USA) as well as the northwestern Atlantic (Newfoundland and Quebec, Canada). We developed harbour seal-specific primers to investigate the potential impact of POP exposure on the expression of eight important genes. We found correlations between the blubber mRNA levels of three of our eight target genes and the dominant persistent organic pollutant in seals [polychlorinated biphenyls (PCBs)] including estrogen receptor alpha (Esr1: r 2 = 0.12, p = 0.038), thyroid hormone receptor alpha (Thra: r 2 = 0.16; p = 0.028), and glucocorticoid receptor (Nr3c1: r 2 = 0.12; p = 0.049). Age, sex, weight, and length were not confounding factors on the expression of genes. Although the population-level consequences are unclear, our results suggest that PCBs are associated with alterations of the expression of genes responsible for aspects of metabolism, growth and development, and immune function. Collectively, these results provide additional support for the use of harbour seals as indicators of coastal food-web contamination.

PBDEs and PCBs in the liver of the St Lawrence Estuary beluga (Delphinapterus leucas): a comparison of levels and temporal trends with the blubber.

Due to their lipophilic properties, persistent organic pollutants (POPs) are commonly assessed using the blubber of marine mammals. However, these chemicals are also accumulating in other tissues including the liver. Some pollutants, namely perfluorinated alkyl acids, are found predominately in the liver and blood of marine mammals, and thus monitored in those tissues. This raises the question whether any tissue would represent an identical trend of POPs in the SLE beluga. The current study reports the first temporal trends of PBDEs and PCBs in the liver of 65 SLE belugas. Neither ∑7PBDEs nor major individual PBDE-homolog group concentrations showed significant trends between 1993 and 2007. Also, ∑32PCBs did not change over years, although, tetra-, penta- and hepta-PCB decreased by 7.1, 6.8 and 8.5%, respectively, in males, whereas tetra-, penta- and octa-PCBs declined by 11, 12 and 12.9%, respectively, in females. In order to compare the distribution of POPs between liver and blubber, a lipid normalised concentration ratio R (blubber/liver) for PBDEs and PCBs was calculated for each individual beluga. For all PBDE and several PCB homolog groups, mean R values were not statistically different from unity indicating that the partitioning of these POPs is governed by the tissue lipid-content. Temporal trends of R ratios of PBDEs and PCBs were also examined. There were generally no significant temporal trends except for PBDEs in males where R increased in average by 12.7 ± 2.9% yearly. The stratification of the blubber into a metabolically active (inner) and less active layers (outer blubber) may result in a slower response time of the blubber (full depth) than the liver to the recent change of contamination in the environment and explain the time trend differences between both tissues. This study suggests that the liver is more representative of recent exposure to lipophilic contaminants.

Large and growing environmental reservoirs of Deca-BDE present an emerging health risk for fish and marine mammals.

Polybrominated diphenyl ethers (PBDEs) have been the subject of intense scientific and regulatory scrutiny during recent years. Of the three commercial forms (Penta, Octa and Deca) of PBDEs that have been widely used as flame retardants in textiles, furniture upholstery, plastics, and electronics, only Deca-BDE remains on the general market in North America, while a recent ruling of the European Court spells an impending end to its use in Europe. We review here highlights of aquatic research documenting the rapid emergence of PBDEs as a high priority environmental concern in Canada. PBDEs are being introduced in large quantities to the aquatic environment through sewage discharge and atmospheric deposition. In certain environmental compartments, the single congener BDE-209, the main ingredient in the Deca-BDE formulation, has surpassed the legacy PCBs and DDT as the top contaminant by concentration. Limited biomagnification of BDE-209 in aquatic food webs reflects its high log K(ow) and preferential partitioning into the particle phase. As a result, large environmental reservoirs of BDE-209 are being created in sediments, and these may present a long-term threat to biota: BDE-209 breaks down into more persistent, more bioaccumulative, more toxic, and more mobile PBDE congeners in the environment.

Investigations on the sorption of a toxaphene model congener, the B7-1450, on marine sediments.

Sorption is a natural process that takes place in sediments or soils and changes the mobility and availability of hydrophobic organic compounds, such as toxaphene pesticide in the environment. The sorption of the 2-exo,3-endo,5-exo,8,9,10,10-heptachlorobornane (B7-1450), used as a model compound of the toxaphene heptachlorobornane congeners found in sediments, was investigated for the first time through a series of batch sorption experiments. The losses of B7-1450 due to adsorption onto glass walls and to evaporation occurring during analytical treatment steps were corrected. The study showed that these specific losses ranged from 2% to 3.5% for the glass walls adsorption and can be as high as 15% for the evaporation treatment. The sorption coefficients, K(d) and K(oc), of B7-1450 could be overestimated by >30%, particularly for low-concentration samples, if the losses were not corrected. Loss correction equations were established, validated and applied to determine sorption coefficients for the B7-1450 congener. The K(oc) values for B7-1450 determined over a gradient of concentrations ranged from 3.5x10(4) to 6.5x10(4)mlg(-1), revealing a strong affinity of B7-1450 for marine sediments.

Effects of salinity on sublethal toxicity of atrazine to mummichog (Fundulus heteroclitus) larvae.

In coastal marshes, fish larvae may be exposed simultaneously to extreme salinities and to atrazine, a widely used herbicide. To assess the effects of salinity on the toxicity of atrazine, newly-hatched mummichog (Fundulus heteroclitus) were exposed to atrazine (0, 5, 50 and 500 microg/L) at three salinities (3, 15 and 35PSU). Whole body cortisol was measured after 24 h. Body length, condition factor, whole body proteins, lipids, residual masses and water contents were assessed after 96 h. Significants effects were found for both condition factor and water content. Condition factors were lower at salinity 3 and 35 compared to near isoosmotic salinity, 15PSU. In addition, atrazine decreased condition factor at 500 microg/L. Reduction in condition was likely due to retardation in axial growth since body length, percentages of proteins or lipids were not affected. In the absence of atrazine, salinity had no effect on the prevalence of dehydrated (81% water) or hyperhydrated (85% water) larvae. In larvae exposed to atrazine, the prevalence of hyperhydrated larvae increased at 3PSU and 5 microg/L atrazine and that of dehydrated larvae increased at 15 and 35PSU and 5 microg/L atrazine. Severity of dehydratation increased with atrazine concentration at salinity 35PSU. Thus, a short-term exposure to environmentally realistic concentrations of atrazine affects osmotic control in mummichog larvae with possible effects on buoyancy, survival and recruitment.

Temporal trends (1987-2002) of persistent, bioaccumulative and toxic (PBT) chemicals in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada.

Temporal trends of persistent, bioaccumulative and toxic (PBT) chemicals were examined in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Canada. Blubber samples of 86 adult belugas were collected from animals stranded on the shore of the SLE between 1987 and 2002 and analyzed for several regulated PBTs, including polychlorinated biphenyls (PCBs), p,p'dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordane (CHL) and related compounds, hexachlorocyclohexane (HCH) isomers, hexachlorobenzene (HCB) and Mirex. In addition, time trends of tris(4-chlorophenyl)methane (TCPMe) and tris(4-chlorophenyl)methanol (TCPMOH), two compounds that may origin from DDT formulations, were also examined. Concentrations of most of the PBTs examined had exponentially decreased by at least a factor of two (half-life time (t(1/2))<15 years) in beluga between 1987 and 2002 while no increasing trends were observed for any of the PBTs measured. The decreasing trends of PBT concentrations in SLE beluga may be due to a decline in contamination of its diet following North American and international regulations on the use and production of these compounds or by a change in its diet itself or by a combination of both. Some PBTs did not exhibit any significant trends in beluga possibly because the most intense elimination phase subsequent to legislative regulations occurred prior to the 1987-2002 time period. Other chemicals, such gamma-HCH, did not significantly decrease likely because they are still currently used in some restricted applications. Conversely, alpha-HCH showed a significant decreasing trend indicating that SigmaHCHs is not representative of all HCHs. Both TCPMe and TCPMOH exhibited no trends in beluga during the time period examined. The metabolic capacity of SLE beluga has apparently accelerated the depletion of at least one PBT, namely CB-28/31. A significant relationship between the half-life of PBTs in beluga and log Kow was observed for most of the chemicals examined. Several factors are expected to have influenced the temporal changes of PBT concentrations in beluga which limit the usefulness of this species as a bioindicator of changes in PBT contamination in the SLE ecosystem.

Determination of linear and cyclic volatile methylsiloxanes in blood of turtles, cormorants, and seals from Canada.

We measured the concentrations of linear and cyclic volatile methylsiloxanes (VMS) concentrations in the blood plasma of turtles, cormorants, and seals collected from Canadian freshwater and marine ecosystems. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed to quantify the levels of linear and cyclic VMS in the plasma samples. The cyclic VMS of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were present in the plasma of all three species. Linear VMS compounds were observed only in seal plasma from one contaminated site. There was no statistically significant difference among species and locations for D3, D4, and D6 concentrations. Average D5 concentrations ranged from 0.143 to 7.39ngg-1; these concentrations appeared to be associated with diffuse/urban sources. Snapping turtles, cormorants, and seals all exhibited elevated D5 concentrations in contaminated sites relative to the reference sites. Our data indicate that local urban sources of VMS contributed significantly to the observed D5 concentrations in free-ranging wildlife. The presence of cyclic VMS in the plasma of the three species from Canada demonstrates that these chemicals are ubiquitous in aquatic biological systems. This finding raises concerns regarding their persistence in freshwater and marine environments. To the best of our knowledge, this study reports the first measurements of VMS compounds in the plasma of reptiles, birds, and mammals.

Organohalogen contaminants and metabolites in beluga whale (Delphinapterus leucas) liver from two Canadian populations.

Contaminants described as organochlorines (OCs; e.g., polychlorinated biphenyls [PCBs]) are present in tissues of marine mammals, including beluga whales (Delphinapterus leucas), but the complexity of contaminant exposure often is not fully known. The PCBs, OC pesticides, polybrominated diphenyl ether (PBDE) flame retardants, methylsulfonyl (MeSO2)- and hydroxy (OH)-PCB metabolites, and OH-PBDEs and methoxylated (MeO)-PBDEs were determined in the liver of beluga whales from two Canadian populations: the St. Lawrence Estuary (SLB; n=6), and western Hudson Bay in the Canadian Arctic (CAB; n=11). The sigmaPCB, sigmaDDT, and sigmaPBDE concentrations were higher (p < 0.05) in SLB versus CAB. Of 18 detectable OH-PCBs in SLB (mainly 4-OH-CB107, 4-OH-CB112, and 4'-OH-CB120), only 4'-OH-CB120 was found in CAB. The sigmaOH-PCB concentrations were less than 0.2% of the sigmaPCBs in both populations but were higher (p < 0.05) in SLB (65 +/- 22 ng/g lipid wt) than in CAB (3.1 +/- 0.5 ng/g lipid wt). The sigmaMeSO2-PCB concentrations were higher in SLB (3801 +/- 1322 ng/g lipid wt) relative to CAB (77 +/- 23 ng/g lipid wt) and were 11 and 4%, respectively, of the sigmaPCB concentrations. Of the 15 OH-PBDEs, only two congeners were detectable, but not quantifiable (notably 2'-OH-BDE 68 and 6-OH-BDE 47), in animals from both populations. Of the 15 MeO-PBDEs, 4'-MeO-BDE 17 and 6-MeO-BDE 47 in the SLB (n=2) and 2'-MeO-BDE 68 and 6-MeO-BDE 47 in the CAB (n=2) had concentrations from 20 to 100 ng/g lipid weight. The OH-PBDEs and MeO-PBDEs most likely are of natural origin and accumulated in beluga whales, whereas the OH-PCBs and MeSO2-PCBs are metabolites derived from accumulated PCBs. Canadian beluga whale liver contains previously unidentified organohalogen contaminants and metabolites and, thus, a complexity of contaminant exposure that may be impacting the health of Canadian beluga whale populations.

Temporal variations in embryotoxicity of Lake Ontario American eel (Anguilla rostrata) extracts to developing Fundulus heteroclitus.

The recruitment of American eel (Anguilla rostrata) juveniles to Lake Ontario (LO), Canada has declined significantly since the 1980s. To investigate the possible contribution of maternally-transferred persistent organic pollutants (POPs) to this decline, this study measured temporal variations in the toxicity of complex organic mixtures extracted from LO American eels captured in 1988, 1998 and 2008 to developing Fundulus heteroclitus exposed by intravitelline (IVi) injection. The 1988 and 1998 eel extracts were most toxic, causing a pattern of sublethal embryotoxic responses similar to those previously reported in F. heteroclitus embryos exposed to single dioxin-like compounds (DLCs): stunted growth, craniofacial deformities, EROD activity induction, and reduced predatory capacities. The potency of extracts declined over time; the only significant effect of the 2008 eel extracts was EROD induction. The chemically-derived TCDD-TEQs of eel extracts, calculated using measured concentrations of some DLCs and their relative potencies for F. heteroclitus, overestimated their potency to induce EROD activity possibly due to interactions among POPs. Other POPs measured in eel extracts (non-dioxin-like PCBs, PBDEs and organochlorinated pesticides) did not appear to be important agonistic contributors to the observed toxicity. The toxicity of the complex mixtures of POPs measured in LO eels may have been underestimated as a result of several factors, including the loss of POPs during extracts preparation and a focus only on short-term effects. Based on the model species examined, our results support the hypothesis that contamination of LO with DLCs may have represented a threat to the American eel population through ecologically-relevant effects such as altered larval prey capture ability. These results prioritize the need to assess early life stage (ELS) toxicity of DLCs in Anguilla species, to investigate long-term effects of complex eel extracts to ELS of fish, and to develop biomarkers for potential effects in eel ELS sampled in the field.

Low hepatic ethoxyresorufin-O-deethylase activity correlates with high organochlorine concentrations in Atlantic tomcod from the Canadian east coast.

A suppression of hepatic ethoxyresorufin-O-deethylase (EROD) activity was reported recently in large-sized Atlantic tomcod (Microgadus tomcod) from the St. Lawrence Estuary (SLE; QC, Canada), possibly related to chronic exposure to persistent contaminants and/or to emaciation. In the present study, hepatic concentrations of organochlorine contaminants and biological responses were measured in female tomcods from three estuaries located on the Canadian east coast: The SLE, the Miramichi (ME), and the Richibucto (RE) Rivers Estuaries (NB, Canada). Tomcods from the SLE had higher hepatic concentrations of organochlorine contaminants than tomcods from the ME and RE. For example, concentrations of polychlorinated biphenyls (PCBs, lipid wt) were 2.5 to 4 times higher, and concentrations of mirex and chlordanes were 6 times higher, in tomcods from the SLE than in tomcods from the other sites. Concentrations of polycyclic aromatic hydrocarbons (PAHs) metabolites in the bile did not differ among sites. The pattern of biological responses differed markedly between the SLE and the two other sites. Tomcods from the SLE had 1.5 times higher concentrations of DNA adducts and 2 times higher rates of hepatocellular proliferation, but 20 times lower hepatic EROD activity, than tomcods from the ME and RE. Lipid content was not correlated with EROD activity, indicating that low hepatic lipid content alone does not cause suppression of EROD activity in Atlantic tomcod. In contrast, for the three sites combined, EROD activity decreased as concentrations of PCBs increased. Within sites, hepatic PCB concentrations increased as lipid content decreased. This study supports the hypothesis that low EROD activity in SLE tomcods is related to chronic exposure to organochlorine contaminants.

Sorption and competition of two persistent organic pesticides onto marine sediments: Relevance to their distribution in aquatic system.

Sorption is a key process in the distribution of substances between environmental compartments in marine ecosystems. Two persistent organic pesticides, also known as toxaphene congeners, namely B8-1413 (P26) and B9-1679 (P50), are of special interest because they are not detected in sediments while relatively concentrated in marine mammals. Sorption-desorption, entrapment and competition behaviors of these pesticides onto marine sediments were studied to explain their environmental distribution. Data obtained under marine experimental conditions were fitted to sorption models to evaluate sorption coefficients and to assess the degree of B8-1413/B9-1679 entrapment of the two toxaphene congeners in sediments. Carbon normalized sorption coefficients (Koc) of both congeners were similar under in cold (2°C) marine (30 psu) conditions with high values ranging from 1.53×10(5) to 3.28×10(5) mL g(-1)indicative of a strong affinity to marine sediments However, the sorption-desorption investigations indicate that B8-1413/B9-1679 were on average 2.5 times less entrapped in sediments compared to B7-1450, a toxaphene congener known to accumulate predominantly in sediments. These results suggest that the low entrapment of B8-1413 and B9-1679 favor their availability and transfer to biological matrices.

Trends of persistent organic pollutants in American eel (Anguilla rostrata) from eastern Lake Ontario, Canada, and their potential effects on recruitment.

This study reports the history of contamination of American eels (Anguilla rostrata) from eastern Lake Ontario (LO) by persistent organic pollutants (POPs). Three groups of 10 large female eels captured in eastern LO in each of 1988, 1998, and 2008 were analysed for polychlorinated dibenzo-p-dioxins and furans, polychlorinated biphenyls, several organochlorine pesticides, and polybrominated diphenyl ethers. Mean concentrations were up to 3-fold lower in 2008 compared to previous years. When combined with the results of previous studies, these data show that concentrations of POPs in American eels have declined exponentially since the early 1980s by an average of 9.1±1.9% per year. Toxic equivalent (TEQ) concentrations of dioxin-like compounds (DLCs) were calculated from fish toxic equivalency factors. Assuming an efficient transfer of DLCs to their eggs, egg TEQs prior to 2000 exceeded the threshold for chronic toxicity to embryos of European eels (Anguilla anguilla) and lake trout (Salvelinus namaycush) (4-5 pg/g ww of TEQ). These results suggest that embryotoxicity of maternally-derived DLCs from LO eels, historically a major contributor to the spawning stock of American eels, could have impaired the reproductive and recruitment success of the species.

Levels and trends of polybrominated diphenylethers and other brominated flame retardants in wildlife.

In this paper, we review the available data for polybrominated diphenylethers (PBDEs) and other flame retardants in wildlife, with the exception of fishes from Europe and North America which are covered in more detail elsewhere. More data are available for PBDEs than for other compounds, and these show that some of these compounds have become widely distributed in the environment, being found in samples from Europe, Australia, Azerbaijan, North America and the Arctic. Most available data relate to birds and their eggs and marine mammals, but the results of two food web studies are also included. The detection of PBDEs in pelagic marine mammals which feed in deep offshore waters, including baleen whales, indicate that these compounds have found their way into deep-water, oceanic food webs as well as the coastal/shallow sea examples described in detail. In the North Sea study, the most marked increase in lipid-normalised concentrations of six BDE congeners occurred during transfer from predatory fish to marine mammals. In the St. Lawrence Estuary study, marked differences in the ratios observed between species suggested that some fish species may be able to metabolise BDE99.A number of time trend studies have also been conducted, notably in guillemot eggs from Sweden (1969-2000), beluga whales from the Canadian Arctic (1982-1997 and 1989-2001) and from the St. Lawrence Estuary (1988-1999), and ringed seals from the Canadian Arctic (1981-2000). In the temperate latitudes, from these and other studies (e.g. in dated sediment cores), PBDE concentrations began to rise earlier than in those from high latitudes, in line with data for production and use. These trends have now slowed in many cases. Declines could be expected in Europe for many congeners following the cessation of manufacture and use of the penta-mix formulation in the EU, though these are not yet apparent in environmental samples. In Arctic biota, however, the rapidly rising concentrations seen currently in Canada could be expected to continue for some time, reflecting continued production and use of the penta-mix formulation in North America (>95% of the world total) and the impact of long-range atmospheric transport.

Characterization and profiling of hepatic cytochromes P450 and phase II xenobiotic-metabolizing enzymes in beluga whales (Delphinapterus leucas) from the St. Lawrence River Estuary and the Canadian Arctic.

Cytochromes P450 (CYP, phase I) and conjugating (phase II) enzymes can be induced by and influence the toxicokinetics (metabolism) and toxicity of xenobiotic contaminants in exposed organisms. Beluga whale (Delphinapterus leucas) from the endangered St. Lawrence (SL) River Estuary population exhibit deleterious health effects and various severe pathologies that have been associated with contaminant exposure. In contrast, such effects (e.g. reproductive and immunological impairment) are generally less frequent in less exposed populations in the Canadian Arctic (CA). In the present study, opportunistic sampling resulted in the collection immediately after death of liver tissue from a single female neonate SL beluga (SL6) and male and female CA beluga (n=10) from the Arviat region of western Hudson Bay, in addition to sampling of stranded carcasses of male and female SL beluga (n=5) at least 12 h postmortem. We immunologically characterized cross-reactive proteins of hepatic microsomal CYP1A, CYP2B, CYP3A, CYP2E, epoxide hydrolase (EH) and uridine diphosphoglucuronosyl transferase (UDPGT) isozymes. Cross-reactive proteins were found in all SL and CA beluga using anti-rat CYP1A1, anti-rainbow trout CYP3A, anti-human CYP2E1, anti-rabbit EH and anti-human UDPGT1A1 polyclonal antibodies (Abs), whereas faintly cross-reactive CYP2B proteins were only found in SL6 and the CA samples using an anti-rabbit CYP2B1 Ab. In corresponding catalytic activity assessments, only SL6 and all CA beluga microsomal samples exhibited CYP1A-mediated 7-ethoxyresorufin O-deethylase (EROD) activity (51-260 pmol/mg/min), CYP3A-mediated activity (113-899 pmol/mg/min) based on the formation of 6beta-hydroxytestosterone using a testosterone hydroxylase assay, and UDPGT activity (830-4956 pmol/mg/min) based on 1-naphthylglucuronide formation. The marginal cross-reactivity with the anti-CYP2B1 Ab and lack of catalytically measurable hydroxytestosterone isomers associated with CYP2B-type activity in all the SL and CA animals is suggestive of low CYP2B-type enzyme expression in beluga. The absence of measurable total P450 enzyme levels and catalytic activities in samples from the stranded SL belugas suggested catalytically inactive enzymes as a consequence of tissue degradation related due to the time delay of sample collection after death. However, all SL and CA animals demonstrated similar, immunologically cross-reactive phase I and II hepatic enzyme profiles, which is suggestive of the importance of metabolism in the toxicokinetics and fate of xenobiotics in animals from both populations

PCBs and OCPs in male harbour, grey, harp and hooded seals from the Estuary and Gulf of St Lawrence, Canada.

Blubber samples from adult male harbour seals (Phoca vitulina) from the St Lawrence Estuary, and from grey (Halichoerus grypus), harp (Phoca groenlandica) and hooded (Cystophora cristata) seals from the Gulf of St Lawrence, were analysed for polychlorinated biphenyls (PCB) and organochlorinated pesticides (OCP). All seals were between 5 and 19 years of age, and mean ages were not statistically different among the seal species. Mean concentrations of sigmaPCB and mirex were significantly higher in harbour seals, while sigmaDDT concentrations were significantly higher in hooded seals than in the other species examined. Harbour and hooded seals had similar concentrations of sigmaCHLOR, which were higher than in grey and harp seals. SigmaHCH concentrations were significantly higher in harp seals than in harbour and hooded seals and they were significantly higher in harbour and grey seals than in hooded seals. Harp and grey seals had similar levels of HCB, which were significantly higher than in either hooded or harbour seals. Patterns of PCB congeners and individual OCPs varied considerably between the four species. In PCA plots harbour, harp and hooded seals were well separated from each other, while grey seals were separated from the other species by a smaller degree. Between species variations may be explained by their dissimilar migratory patterns, habitat use and proximity to sources of industrial and agricultural pollution, their dietary regime (trophic level and individual prey items) as well as possible variations in the seals' abilities to eliminate these compounds.

Chlorobenzenes, chlorinated pesticides, coplanar chlorobiphenyls and other organochlorine compounds in Greenland biota.

This paper summarises the levels and composition of chlorobenzenes, chlorinated pesticides, coplanar polychlorinated biphenyls (PCBs) and the chlorinated compounds octachlorostyrene (OCS), hexachlorocyclobutadiene (HCBD) and pentachloro-anisole (PCA) in biota from the terrestrial, freshwater and marine environment of Greenland. The data were obtained during the second phase of the Arctic Monitoring and Assessment Programme (AMAP). Of the chlorobenzenes, hexachlorobenzene was the main constituent detected in almost all samples. The chlorobenzenes accumulate in the marine food web in a similar manner to the better-studied persistent organic pollutants, with maximum concentrations in beluga, minke whale and narwhal. However, concentrations in ringed seals and kittiwakes were lower than in marine fish, contradicting biomagnification. Of the organochlorine pesticides, the drin pesticides (aldrin, endrin, dieldrin) and heptachlor had increasing concentrations along the food chain, whilst biomagnification was less pronounced for endosulfan, methoxychlor and mirex. Endosulfan and methoxychlor are pesticides still in use and considered less persistent than other organochlorine pesticides. Their occurrence in Arctic biota is of particular concern, also given the high acute toxicity of endosulfan to fish. Chlorobenzene and pesticide concentrations tended to be lower in the Greenland samples than in the same animals from the Canadian Arctic, whilst their concentrations were similar to samples from Svalbard and Iceland. However, temporal trends might overlap the geographical differences. Coplanar chlorobiphenyls (CBs) were found in all samples analysed, with the maximum concentrations found in marine mammals such as beluga and narwhal. Biota from the terrestrial environment appeared to be less contaminated. The main contributor on a TEQ basis was CB126. OCS, HCBD and PCA were detected in biota from Greenland, although at very low concentrations. OCS seems to have the widest occurrence and the highest potential for biomagnification of the three compounds analysed.

Analysis of six relevant toxaphene congeners in biological samples using ion trap MS/MS.

The quantification of six polychlorinated bornanes (CHBs) was studied using ion trap MS/MS. The significance of the selection of parent ions (Ip) and daughter ions (Id) on the detection of these toxaphene congeners was assessed in standard solution and biological samples. Our results indicate that different Ip and Id, selected at either low or high mass-to-charge (m/z) ratios, influence drastically the response factor of the CHBs and the chemical noise observed. For the octachlorinated toxaphene congeners (Parlar-26 (P-26), Parlar-40/41 (P-40/41), Parlar-44 (P-44)), the detection performance of the ion trap MS/MS is similar whether Ip and Id were chosen at low or high m/z ratios. However, the selection of Ip and Id at high m/z ratios clearly enhances the detection of the nonachlorinated toxaphene congeners (Parlar-50 (P-50), Parlar-62 (P-62)). The improved method, which selects Ip and Id at low m/z ratios for P-26, P-40/41 and P-44 and at high m/z ratios for P-50 and P-62, permitted to obtain low detection limits as well as repeatable and accurate results.

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.

Sorption behaviors of a persistent toxaphene congener on marine sediments under different physicochemical conditions.

Sorptive processes are important parameters affecting the mobility, availability and fate of persistent organic pollutants (POPs), such as toxaphene, in aquatic systems. The sorption and desorption behaviors of the B7-1450, a stable toxaphene congener in environment, on marine sediment was studied under different temperature and salinity conditions to better understand the B-1450 distribution in estuarine systems. The data were fitted to different sorption models to characterize sorption behaviors by evaluating sorption coefficients and sequestrated fraction of B7-1450 on sediments. High carbon-normalized sorption coefficients (Koc) of the B7-1450 were observed with values ranging from 3.2×104 to 6.0×104 mL g(-1) under experimental conditions. The data showed an increase of B7-1450 sorption coefficients with the salinity and a decrease with temperature. These investigations indicate that B7-1450 is three times more sequestred on sediments in cold (2°C, 30 psu) than in warm marine conditions (20°C, 30 psu). These results suggest that the mobility and bioavailable of B7-1450 or other POPs from the sediments could be less important in cold marine comparatively in warm marine and warm freshwater media. As a result of climate changes, the warming of mid and high latitudes coastal waters could enhance the mobility of POPs.

Qualitative analysis of halogenated organic contaminants in American eel by gas chromatography/time-of-flight mass spectrometry.

Target compound analysis with scanning mass spectrometers such as quadrupole or magnetic sector instruments is used extensively in environmental chemistry because of the selectivity, sensitivity, and robustness. Yet, target compound analysis selectively ignores the majority of compounds present in a sample, especially in complex matrices like fish. In this study, time-of-flight mass spectrometry was used to screen for and identify halogenated compounds in American eels (Anguilla rostrata). Individual and then pooled eel samples were analysed using electron ionization and electron capture negative ionization (ECNI) modes. Eels were differentiated by principal component analysis of chemical profiles and were grouped corresponding to their capture location, all with a single instrument injection per sample. Bromine containing compounds were further investigated by taking advantage of the selectivity of ECNI by utilizing the Br(-) ion m/z 79 and 81. A total of 51 brominated compounds were detected and their identities were attempted by authentic standards, library searching, and/or chemical formula prediction based on accurate mass measurements. Several PBDEs were identified in the samples, and the majority of the non-PBDEs identified were bromophenols, bromoanisoles, and bromobenzenes. These classes of compounds are synthesized for use in flame retardant production either as intermediates or as final products. However, their occurrence in eels was most likely the result of metabolism or break-down products of high production volume flame retardants like polybrominated diphenyl ethers and bromophenoxy compounds.