Levels and patterns of persistent organochlorines in minke whale (Balaenoptera acutorostrata) stocks from the North Atlantic and European Arctic

Regional variation in PCBs and organochlorine (OC) pesticide concentrations was examined using the blubber of 155 minke whales (Balaenoptera acutorostrata) sampled in seven regions in the North Atlantic and European Arctic, including western and southeastern Greenland, the Norwegian Sea, the North Sea and the Barents Sea. The levels and relative proportions of OCs were also used to examine the boundaries for North Atlantic minke whale stocks previously defined by the International Whaling Commission (IWC). Concentrations of major OC groups (sigmaPCB, 89.1-22 800 ng/g lipid; sigmaDDT, 65.3-6280 ng/g lipid; sigmaCHL, 33.3-2110 ng/g lipid) generally increased from west to east, while HCH concentrations (sigmaHCH, < 1-497 ng/g lipid) showed the opposite trend. Statistical comparison between six regions using sex-adjusted least squared mean concentrations showed that minke whales from the Barents Sea had significantly higher concentrations of EPCBs than those from the Vestfjorden/Lofoten, the North Sea, and west Svalbard, as well as significantly higher sigmaDDT concentrations compared to west Greenland animals. The differences in concentrations suggest that west and southeast Greenland minkes may represent one group of whales, which are distinct from both the Jan Mayen minkes and those from other IWC defined stocks in northern European waters. Principal components analysis using proportions of 71 PCB congeners and 20 OC pesticides (of total OCs) did not reveal any major differences among groups although minkes from the North Sea were distinguished from those from Greenland waters by higher loadings of more highly chlorinated PCBs and recalcitrant OC pesticides. The general similarity in mean levels of sigmaPCBs, sigmaDDT and sigmaCHL, as well as mean principal components analysis scores, among minkes sampled at Jan Mayen, Svalbard, Vestfjorden/Lofoten, the North Sea and the Barents Sea suggests that the whales are quite mobile and may feed in multiple areas within the northeastern Atlantic.     

Organochlorine contaminants in northeast Atlantic minke whales (Balaenoptera acutorostrata)

Blubber samples of 72 minke whales (Balaenoptera acutorostrata) were obtained from the northeast Atlantic in July and August 1992, and evaluated for organochlorine contamination. The following organochlorines were determined: the industrial chemicals PCBs (polychlorinated biphenyls), and the organochlorine pesticides DDTs (dichlorodiphenyltrichloroethanes), HCHs (hexachlorocyclohexaneb), HCB (hexachlorobenzene) and CHLs (chlordanes). The concentrations of SigmaPCB (sum of concentrations of 18 PCB congeners) and SigmaDDT (sum of concentrations of p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT and o,p'-DDD) ranged from 0.6-20.8 and 0.5-14.8 microg g(-1) lipid weight, with mean concentrations at 3.8 and 2.5 microg g(-1) lipid weight, respectively. The mean concentrations of HCB, the chlordane metabolites oxychlordane, cis-chlordane and trans-nonachlor, and the HCH isomers (alpha-, beta- and gamma-HCH) were all < 1 microg g(-1) lipid weight. Significantly higher concentrations of the three major pollutants (SigmaPCB, SigmaDDT and SigmaCHL) were found in mature males as compared to mature females and juveniles of both sexes. No such relationship was found for SigmaHCH and HCB. Stomach contents of northeast Atlantic minke whales indicate considerable heterogeneity in the diet when comparing different years, seasons and geographical areas. However, without knowing more about the minke whale migration pattern, or possible geographical segregation with age and sex, the interchemical variation of organochlorines between sampling areas may not reflect true geographical differences.     

Concentrations and accumulation patterns of organochlorine contaminants in the blubber of harbour porpoises, Phocoena phocoena, from the coast of Newfoundland, the Gulf of St Lawrence and the Bay of Fundy/Gulf of Maine

Concentrations of 99 organochlorine compounds were measured in the blubber of 196 harbour porpoises, Phocoena phocoena, killed in commercial gill net fisheries in the western North Atlantic. PCBs and chlorinated bornanes (CHB) were the dominant contaminants in all porpoises. Mean concentrations (with standard deviations) of PCBs and CHBs from the three regions were as follows: Bay of Fundy/Gulf of Maine, PCB males 17.3 +/- 11.2 microg/g, PCB females 11.4 +/- 4.8 microg/g, CHB males 11.5 +/- 6.6 microg/g, CHB females 8.4 +/- 5.3 microg/g; Gulf of St Lawrence, PCB males 10.6 +/- 5.4 microg/g, PCB females 7.2 +/- 3.9 microg/g, CHB males 14.1 +/- 8.8 microg/g, CHB females 9.0 +/- 6.3 microg/g; southeast Newfoundland, PCB males 5.2 +/- 2.5 microg/g, PCB females 5.5 +/- 4.4 microg/g, CHB males 7.0 +/- 2.2 microg/g, CHB females 5.5 +/- 3.0 microg/g. The relative composition of the major contaminant groups found in male and female harbour porpoise blubber from the three locations varied. In order of decreasing concentration, porpoises from Fundy/Maine had PCBs > CHB > DDT > chlordanes (CHL), whereas Gulf of St Lawrence and Newfoundland porpoises had CHB > PCB > DDT > CHL. Significant increases with age were observed for most contaminants in male harbour porpoises, and significant decreases were observed in females. Females lose about 15% of their contaminant burden per birth. PCB and DDT levels in porpoises from the Bay of Fundy are significantly lower than those recorded in the 1970s.     

Can seal eating explain elevated levels of PCBs and organochlorine pesticides in walrus blubber from eastern Hudson Bay (Canada)?

Walrus (Odobenus rosmarus) blubber samples from Inukjuak and Akulivik (East Hudson Bay), Foxe Basin (Igloolik and Hall Beach) and Loks Land (East Baffin Island) were analysed for PCB congeners (ortho and non-ortho substituted) and other persistent organochlorines (DDT, toxaphene, chlordanes, dieldrin, mirex), as well as chlorinated dioxins/furans, to document spatial trends in contaminants in Canadian Arctic marine biota. Samples from 19 of 53 individuals had concentrations of SigmaPCBs greater than 1000 ng g(-1) (wet wt); the remaining individuals had much lower concentrations (50-600 ng g(-1)). Highest concentrations were found in samples from Inukjuak where average concentrations in blubber of females (N = 9) were 1450 +/- 954 ng g(-1) toxaphene, 2750 +/- 1780 ng g(-1) SigmaCHLOR, 2160 +/- 925 ng g(-1) SigmaDDT and 4790 +/- 2380 ng g(-1) SigmaPCB. SigmaPCB and SigmaDDT concentrations greater than 1000 ng g(-1) were unexpected based on previous studies of walrus from Greenland and Alaska. Local contamination was ruled out because levels of all organochlorines were elevated in each animal from Inukjuak, and elevated levels were also found in animals from Akulivik and Loks Land. Walrus from Inukjuak had sigma13C and sigma15N values in muscle intermediate between those of ringed seals (Phoca hispida) and those of walrus from Akulivik with low organochlorine levels. There was a weak but significant correlation between and sigma15N and (log)SigmaPCB. The Inukjuak walrus also had higher proportions of highly chlorinated PCB congeners, and higher DDE/SigmaDDT ratios than walrus from Igloolik or Akulivik. The results suggest that the walrus with elevated organochlorines are feeding at a higher trophic level than those with low levels and are probably utilizing ringed seals for a portion of their diet.     

PCBs and organochlorine pesticides in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), 1994-1998

For the first time, organochlorine (OC) contaminants were measured in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), to compare contaminant levels to those previously measured in dead stranded belugas. PCBs, DDTs, toxaphene and chlordane-related compounds were the major OC contaminants detected in 44 belugas biopsied in 1994-1998. SigmaPCB (the sum of 104 congeners) ranged from 2080 to 128,000 ng/g lipid in males (n=34; minimum estimated ages 8-22 years), and from 148 to 44,100 ng/g lipid in females (n=10; minimum estimated ages 7-22 years). The concentrations of PCBs and OC pesticides in the blubber of these whales overlapped those observed in stranded belugas from an earlier study, and demonstrated comparable age and sex-related trends. However, lower proportions of mirex, HCB, DDTs, and many of the highly chlorinated PCBs occurred in the biopsy samples compared to results for blubber from stranded carcasses. Most major OC compounds were present at lower concentrations in the biopsies, but this does not appear to be solely related to age differences between the two groups, or to emaciation in the stranded whales. Nor does it appear to be associated with the use of superficial biopsies, and the possible stratification of lipids and OCs in the blubber layer. Nevertheless, given these possible confounding factors, and the uncertainty in age estimates for the biopsied whales, the results point to the need for careful interpretation of biopsy results when comparing with data taken from the full depth of the blubber mantle in stranded whales. Taken together, results from both biopsied whales and previously studied stranded belugas indicate that PCB and OC pesticide contamination of St. Lawrence beluga whales may occur across a broader range of levels than previously thought, at least for males which formed the largest group in this study, possibly due to different degrees of dietary exposure. It also appears that measuring contaminant concentrations only in stranded whales, may overestimate OC levels in the population as a whole, especially for highly chlorinated OCs.     

Total toxaphene and specific congeners in fish from the Yukon, Canada

Toxaphene is one of the major persistent organic pollutants with global environmental impacts. We have measured total toxaphene and specific congeners concentrations in 19 fish samples collected from the Yukon, Canada using gas chromatography coupled to ion trap MS/MS. The total toxaphene concentrations ranged from 42 to 242 ng/g (mean = 107+/-61 ng/g). The sum of the three specific congeners (Parlar 26, 50 and 62) was within 10-55 ng/g. The ratio of the sum of the three congeners to the total toxaphene varied between 8% and 25% in the fish samples but the ratio may be species specific. Our results suggest that consumption of these Yukon fish should have minimal risk of toxaphene exposure.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--II. Temporal trends, 1982-1994

Blubber samples from 16 dead beluga whales (Delphinapterus leucas) collected during 1993-1994 in the St Lawrence River estuary were analysed for PCB congeners and other persistent organochlorines (DDT-group, chlorinated bornanes (toxaphene, CHB), chlordane SigmaCHL), hexachloro-cyclohexanes (SigmaHCH), chlorobenzenes (SigmaCBz), tris(p-chlorophenyl methane (TPMe) and mirex). Concentrations and relative proportions of major individual organochlorine components were within the same range as previous results for this population. Temporal trends were studied by combining the results with data from the analysis of 44 samples (1986-1990) and (for DDT and Aroclor PCBs only) with 20 samples (1982-1985) reported by Martineau et al., 1987. Results were lipid normalized and then age-adjusted by an ANCOVA model. Significant relationships between age and concentrations of most organochlorine groups were found for females but not for males. Significant declines were observed in SigmaDDT, and Aroclor PCBs (1.5- and 1.9-fold, respectively) in males between the 1982-1985 and 1993-1994 collection periods. Significant declines were also observed for SigmaHCH and SigmaCBz in males between 1986-1988 and 1993-1994. Mean concentrations of CHBs were significantly higher in 1993-1994 than in earlier years while dieldrin, SigmaCHL, mirex, and TPMe showed no trend. Declines in concentrations of major organochlorine groups were not observed in females possibly because of higher year to year, and within year, variation. The temporal trend in DDT and PCB concentrations in male beluga blubber paralleled trends in seals, eels, and seabirds in the St Lawrence estuary observed during the 1980s.     

Polychlorinated biphenyls, organochlorinated pesticides, and polybrominated diphenyl ethers in the cerebral cortex of wild river otters (Lontra canadensis)

We measured the levels of ortho-substituted polychlorinated biphenyls (PCB), organochlorinated pesticides (OCP), and polybrominated diphenyl ethers (PBDE) in the cerebral cortex of river otters (Lontra canadensis) trapped from Ontario and Nova Scotia between 2002 and 2004. The mean concentration of total PCBs was 70.9+/-12.1 ng/g l.w., and congeners 153, 180 and 138 accounted for nearly 60% of the sum. The mean concentration of total OCPs was 21.2+/-3.7 ng/g l.w., and hexachlorobenzene (32.6% of total) and DDE (28.1%) accounted for the majority. The mean concentration of total PBDEs was 3.2+/-0.6 ng/g l.w., and congeners 99 (44.9%), 153 (30.5%), and 100 (24.7%) were measured at the indicated percentages. There was no relationship between these residue data and concentrations of brain mercury or neurochemical receptors and enzymes as determined in earlier studies on these same animals.     

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) in tissues of humans, dolphins, and sharks from the United States

Concentrations of tetrabromobisphenol A (TBBPA) and alpha-, beta-, and gamma-isomers of hexabromocyclododecanes (HBCDs) were determined by liquid chromatography-tandem mass spectrometry (LC-ESI-MS/MS) in human adipose tissue obtained in New York City, and in three marine top-level predators--bottlenose dolphin, bull shark, and Atlantic sharpnose shark--collected from coastal waters of Florida, USA. The overall mean concentrations (mean+/-SD) of TBBPA and HBCDs were 0.048+/-0.102 and 0.333+/-0.571 ng/g lipid wt in human adipose tissue samples, 1.2+/-3 and 7.38+/-18 ng/g lipid wt in bottlenose dolphin blubber, 9.5+/-12 and 77.7+/-128 ng/g lipid wt in bull shark muscle, and 0.872+/-0.5 and 54.5+/-88 ng/g lipid wt in Atlantic sharpnose shark muscle. Overall mean concentrations of HBCDs were 5-10-fold higher than mean TBBPA concentrations, in all of the samples analyzed. The highest concentrations of TBBPA and HBCDs were detected in the bull shark muscle at concentrations of 35.6 and 413 ng/g, lipid wt, respectively. Concentrations of TBBPA and HBCDs, after log-transformation, were significantly correlated with each other in human adipose tissue and bottlenose dolphin blubber, but not in bull shark muscle samples. In the human adipose tissue samples, the concentrations of HBCDs were 3-4 orders of magnitude lower than the concentrations of polybrominated diphenyl ethers (PBDEs) previously reported for the same set of tissue samples. Concentrations of HBCDs in human samples from the United States were 1-5-fold lower than the concentrations reported from several European countries. HBCD concentrations in bottlenose dolphins from the United States were 1-2 orders of magnitude lower than the concentrations reported for other cetacean species from Europe. The present report is the first to determine levels of TBBPA and HBCDs in humans, bottlenose dolphins, and sharks from the United States.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--I. Concentrations and patterns of specific PCBs, chlorinated pesticides and polychlorinated dibenzo-p-dioxins and dibenzofurans

Blubber samples from beluga whales (Delphinapterus leucas) in the St Lawrence River estuary were analysed for PCB congeners (ortho- and non-ortho-substituted) and other persistent organochlorines as well as chlorinated dibenzo-dioxins/furans (PCDD/Fs). Major individual components (mean concentrations > 1 microg g(-1)) were 4,4'-DDE, -DDD and -DDT, T12 (a toxaphene-related compound), trans-nonachlor, oxychlordane, mirex, HCB, tris(p-chlorophenyl) methane and dieldrin. Concentrations of SigmaPCBs (8.3-412 microg g(-1)), SigmaDDT (3.36-389 microg g(-1)) and mirex (0.18-6.8 microg g(-1)) were particularly elevated relative to other odontocetes in Canadian waters. SigmaDDT, PCBs (as Aroclor), mirex and T12 concentrations were positively correlated with age of adult females (> 10 years) but only weakly, or not significantly, correlated with age of adult males. PCDD/Fs were present at low ng kg(-1) levels and consisted mainly of penta- and hexachlorofurans, and hepta- and octachlorodioxin. CB126 (3,3',4,4',5-PCB) was the most prominent non-ortho-substituted PCB congener in beluga blubber. Total TCDD toxic equivalents averaged 330 ng kg(-1) in females and 1400 ng kg(-1) in males and were dominated by CB126, and the mono-ortho-substituted congeners CB105 and CB118. Biomagnification factors (BMFs) for mirex and SigmaPCB from fish to beluga ranged from 11 to 16, and were similar to BMFs in Arctic animals, indicating that elevated levels in St Lawrence animals are a consequence of relatively high levels of recalcitrant organochlorines in prey of the beluga in the St Lawrence river system.     

Polycyclic aromatic hydrocarbons in rainwater and surface waters of Lake Maggiore, a subalpine lake in Northern Italy

Fourteen polycyclic aromatic hydrocarbons (PAHs) were measured in surface waters and precipitation inputs to Lake Maggiore, a subalpine lake in Northern Italy, from July 2003 to January 2004. Particulate and dissolved phases in surface water and rain samples were determined. Analyses of PAHs were performed using XAD-2 resin to isolate the dissolved PAHs and subsequent extraction by accelerated solvent extraction (ASE). Both the dissolved and particulate phase PAH patterns in surface water and rainwater samples were dominated by the low molecular weight compounds (e.g., phenanthrene, fluoranthene and pyrene). More than 85% of PAHs in surface waters and 72% of PAHs in rainwater were associated to the dissolved phase. The SigmaPAH concentrations in surface waters (particulate and dissolved phases) were 0.584 +/- 0.033 ng l(-1), 2.9 +/- 0.312 ng l(-1) and in rainwater (particulate and dissolved phases) 27.5 +/- 2 ng l(-1), 75.4 +/- 9 ng l(-1), respectively. Temporal variability of PAH concentrations in rain and surface water samples were observed, with higher concentrations in November and December, coinciding with the largest precipitation amounts. The comparison of PAH signatures in rainwater and surface waters seems to indicate that wet deposition (2.5-41 microg m(-2) month(-1)) is the main source of PAH contamination into surface waters of Lake Maggiore.     

Chemical contaminants in juvenile gray whales (Eschrichtius robustus) from a subsistence harvest in Arctic feeding grounds

Gray whales are coastal migratory baleen whales that are benthic feeders. Most of their feeding takes place in the northern Pacific Ocean with opportunistic feeding taking place during their migrations and residence on the breeding grounds. The concentrations of organochlorines and trace elements were determined in tissues and stomach contents of juvenile gray whales that were taken on their Arctic feeding grounds in the western Bering Sea during a Russian subsistence harvest. These concentrations were compared to previously published data for contaminants in gray whales that stranded along the west coast of the US during their northbound migration. Feeding in coastal waters during their migrations may present a risk of exposure to toxic chemicals in some regions. The mean concentration (standard error of the mean, SEM) of sigmaPCBs [1400 (130) ng/g, lipid weight] in the blubber of juvenile subsistence whales was significantly lower than the mean level [27,000 (11,000) ng/g, lipid weight] reported previously in juvenile gray whales that stranded in waters off the west coast of the US. Aluminum in stomach contents of the subsistence whales was high compared to other marine mammal species, which is consistent with the ingestion of sediment during feeding. Furthermore, the concentrations of potentially toxic chemicals in tissues were relatively low when compared to the concentrations in tissues of other marine mammals feeding at higher trophic levels. These chemical contaminant data for the subsistence gray whales substantially increase the information available for presumably healthy animals.     

Residues of organochlorine pesticides in Alabama soils

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.     

Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

Heavy metals in two populations of North Atlantic fin whales (Balaenoptera physalus)

Concentrations of cadmium, copper and zinc have been analyzed in muscle, liver and kidney tissues of fin whales (Balaenoptera physalus) from two locations in the North Atlantic, Iceland and Spain. The concentrations of zinc in the muscle and that of cadmium in the liver and the kidney were significantly higher in fin whales from Iceland. Other differences between whales from the two areas concern the dynamics of cadmium in the organism. These findings support the hypothesis that fin whales from the two sites belong to different stocks and that cadmium in the organism can be used as a complementary tool in studies of population identity.     

Nonylphenols, nonylphenol-ethoxylates, linear alkylbenzenesulfonates (LAS) and bis (4-chlorophenyl)-sulfone in the German Bight of the North Sea.

Nonylphenols and nonylphenol-ethoxylates were detected in the water and sediment samples from the German Bight of the North Sea. Additionally bis (4-chlorophenyl)-sulfone and linear alkylbenzenesulfonates (LAS) were detected in marine waters. Proof of identification is given by comparison of spectral and chromatographic data from the compounds in sample extracts to those obtained from pure standards. In extracts obtained from water samples taken in 1990 and 1995 the concentrations of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year. The concentrations of nonylphenols in seawater varied from 0.7 to 4.4 ng/l while in the Elbe estuary about 33 ng/l were found. In water samples taken in 1998 nonylphenol-polyethoxylates could not be determined, whereas LAS concentrations of 30 ng/l were confirmed by HPLC-MS/MS. The concentrations of bis (4-chlorophenyl)-sulfone ranged from 0.18 to 2.2 ng/l. In sediment samples LAS concentrations of 39-109 ng/g dry weight were determined.     

Effects of a catalytic converter on PCDD/F, chlorophenol and PAH emissions in residential wood combustion

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.     

Determination of toxaphenes in fish and marine mammals

An analytical method for the determination of toxaphene in biological materials using gas chromatography with an electron capture detector (GC-ECD) has been established and validated for three single congeners (chlorinated bornanes (CHB) 26, 50 and 62). The analytical method was based on a method for determination of PCB, DDT and other chlorinated pesticides. To include toxaphene congeners an extra step, adsorption chromatography on silica columns, was introduced to separate the pesticides from PCB. The recovery of CHB-26, 50 and 62 were 97+/-11%, 94+/-10% and 99+/-12%, respectively. Samples from cod, ringed seal and polar bear from the Norwegian arctic environment have been analysed. The levels of CHB-26 and 50 found were 13-55 ng/g fat in cod, 1.3-7.7 ng/g fat in ringed seal and 0.4-119 ng/g fat in polar bear. The levels of CHB-62 were 2.0-13, 0.8-3.4, 0.2-11 ng/g fat in cod, ringed seal and polar bear, respectively.     

Organochlorine and butyltin residues in walleye pollock (Theragra chalcogramma) from Bering Sea, Gulf of Alaska and Japan Sea

Persistent organochlorine (OC) and toxic butyltin compounds (BTs) were determined in walleye pollock (Theragra chalcogramma) collected from Gulf of Alaska, Bering Sea and Japan Sea, during 1991 and 1992. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and its metabolites were the most abundant compounds ranging up to 3200 and 2500 ng/g on lipid weight, respectively, followed by chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB) in the liver of walleye pollock. Concentrations of HCHs and HCB in walleye pollock from these remote areas were higher than those in fishes from the western North Pacific and Japanese coastal waters, indicating atmospheric transport of these compounds to higher latitude regions such as Bering Sea and Gulf of Alaska and/or local input around northern Japan Sea. The concentrations of other OCs were generally comparable to those in fishes from North Pacific Ocean and Japanese waters but significantly lower than in cod-like fishes from North Atlantic and European countries. Among sampling locations, walleye pollock from Japan Sea showed higher concentrations of DDTs and HCHs compared to fishes from Bering Sea and Gulf of Alaska, suggesting greater input of these compounds around Japan Sea. Slower declining trend of DDTs and CHLs and an increasing pattern of PCBs concentrations were found in walleye pollock from Bering Sea during 1982-1992. This may imply a continuous input of these compounds by long-range transport and/or long-term persistency in these cold regions. Compared to the fishes from Japan Sea, walleye pollock from Bering Sea and Gulf of Alaska showed higher proportions of alpha-HCH and p,p'-DDE in the composition of HCH isomers and DDT compounds, respectively. This suggests selective transportability of these compounds during long-range transport to higher latitude remote areas. Concentrations of tributyltin (TBT) in the muscle of walleye pollock ranged from 1.1 to 5.5 ng/g on wet weight. Concentrations of TBT in deep-sea walleye pollock from Gulf of Alaska and Bering Sea were lower than those in Japan Sea.     

Toxaphene levels in salmon (Salmo salar) from the Baltic Sea

Three toxaphene congeners have been determined in salmon from the Swedish coastal environment using both supercritical fluid (SFE) and the traditional liquid/liquid extractions. The levels obtained using a modifier-free SFE technique, followed by group separation on a silica gel column, were by far much lower than concentrations obtained by SFE with a modifier or liquid/liquid extraction. The mean concentrations on fresh weight basis using a liquid/liquid extraction technique were 5.87, 8.70 and 1.59 microg/kg for CHBs 26, 50 and 62, respectively. There was a plausible relationship between the various fishing sites and the toxaphene levels.