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.     

Profile of persistent chlorinated contaminants,including selected chiral compounds,in wolverine (Gulo gulo) livers from the Canadian Arctic

Wolverines (Gulo gulo) are circumpolar omnivores that live throughout the alpine and arctic tundra ecosystem. Wolverine livers were collected at Kugluktuk (Coppermine), NU (n=12) in the western Canadian Arctic to report, for the first time, the residue patterns of persistent organochlorine contaminants (OCs) in this species. The enantiomer fractions (EFs) of several chiral OCs, including PCB atropisomers, in wolverines were also determined. Results were compared to OC concentrations and EFs of chiral contaminants in arctic fox (Alopex lagopus) from Ulukhaqtuuq (Holman), NT (n=20); a closely related species that scavenges the marine and terrestrial arctic environment. The rank order of hepatic concentrations for sum ( summation operator ) OC groups in wolverines were polychlorinated biphenyls ( summation operator PCB)>chlordane-related components ( summation operator CHLOR)>DDT-related compounds ( summation operator DDT)>hexachlorocyclohexane isomers ( summation operator HCHs). The most abundant OC analytes detected in wolverine liver were PCB-153, PCB-180, and oxychlordane (OXY). Wolverine age and gender did not influence OC concentrations, which were comparable to lipid-normalized values in arctic fox. The EFs of several chiral OCs (alpha-HCH, cis- and trans-chlordane, OXY, heptachlor exo-epoxide) and PCB atropisomers (PCB-136, 149) were nonracemic in arctic fox and wolverine liver and similar to those previously calculated in arctic fox and polar bears from Iceland and the Canadian Arctic. Results suggest that these species have similar ability to biotransform OCs. As well, contaminant profiles suggest that terrestrial mammals do not represent the major source of OC exposure to wolverines and that wolverines are scavenging more contaminated prey items, such as marine mammals. While summation operator PCB did not exceed the concentrations associated with mammalian reproductive impairment, future research is required to properly evaluate the potential affect of other OCs on the overall health of wolverines.     

Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

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.     

Persistent organic pollutants,heavy metals and parasites in the glaucous gull (Larus hyperboreus) on Spitsbergen

The prediction of a higher parasite infection as a consequence of an impaired immune system with increasing persistent organic pollution (POP) and heavy metal levels were investigated in adult glaucous gull (Larus hyperboreus) from Svalbard. The levels of chlorinated pesticides, polychlorinated biphenyls (PCBs), toxaphenes and polybrominated diphenyl ethers (PBDEs) were measured in liver. Cupper, cadmium, lead, mercury, selenium and zinc were measured in kidney samples. An elevated ratio of PCB-118 was found, suggesting that local contamination from the settlement was detectable in the glaucous gull. Eight cestodes, four nematodes, two acanthocephalan and three trematode helminth species were found in the intestine. A positive correlation was found between cestode intensities and selenium levels and between acanthocephalan intensities and mercury levels. No correlation was found between parasite intensities and POP concentrations. It is concluded that the contaminant levels found in glaucous gulls do not cause immune suppression severe enough to affect parasite intensity.     

Fate of permethrin in model outdoor ponds

Abstract

In 1979 and 1980, outdoor artificial ponds were treated with ¹⁴C‐pennethrin (labelled at either the cyclopropyl or methylene position) at 0.028 kg/ha (15 ug/L). Uptake of permethrin by duckweed and hydrosoil was monitored by direct combustion, TLC‐autoradiography, HPLC, and liquid scintillation counting. Rapid loss of permethrin from the waiter coincided with the detection of five degradation products in the water at concentrations below 2.0 ug/L. The products were cis‐ and trans‐cyclopropyl acid, phenoxybenzoic acid, and phenoxybenzyl alcohol, and an unknown non‐cleaved product of permethrin. Permethrin was readily sorbed by duckweed but was not persistent. Permethrin residues in the hydrosoil, which was the major sink for permethrin added to the ponds, were persistent and were detected at 420 days post‐treatment. Cis‐permethrin was more persistent in the hydrosoil than the trans‐permethrin. The results indicated that permethrin in water was short‐lived at an application rate of 15 ug/L because of the rapid degradation of permethrin in the water and sorption of permethrin by the hydrosoil and vegetation. However, at one year post‐treatment, permethrin residues were still detected in the hydrosoil at 1.0 ug/kg.     

Levels and trends of persistent organic pollutants in ringed seals (Phoca hispida) from Central West Greenland, with particular focus on polybrominated diphenyl ethers (PBDEs)

Polybrominated diphenyl ethers (PBDEs) and the organochlorine compounds polychlorinated biphenyls (PCBs), DDTs, HCB, chlordane-related pesticides, HCH and toxaphene were analysed in blubber of juvenile ringed seals from Central West Greenland collected between 1982 and 2006. The longest time series could be established for PBDEs, partly based on archived material, while PCBs and DDTs covered a study period from 1994-2006. All organochlorines showed decreasing trends, most pronounced for DDT and HCH with an annual change of 8%. BDE-47 had a significantly increasing trend of 5% annually. It was the only BDE congener consistently above the detection limit, with annual median concentrations between 0.78 ng/g lw to 3.54 ng/g lw, i.e. about 10 times lower than values from East Greenland observed in a similar time trend study on ringed seal blubber [Rigét F, Vorkamp K, Dietz R, Rastogi SC. Temporal trend studies on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in ringed seals from East Greenland. J Environ Monit 2006; 8: 1000-5]. A clear East>West difference was also found for PCBs and DDTs, but not for chlordanes, toxaphene or HCHs. Sigma 10-PCB, Sigma DDT and Sigma Chlordanes had similar annual median concentrations, typically exceeding SigmaPBDE by two orders of magnitude. The concentrations of HCH and toxaphene were in an intermediate group, with highest annual median concentrations of 135 ng/g lw and 20 ng/g lw, respectively. For most compound groups, the circumpolar trend previously established under for example the Arctic Monitoring and Assessment Programme was confirmed, but apparently, more data are needed for chlordane-related compounds and toxaphene. Statistical analyses of the compound patterns in the ringed seal samples revealed significantly greater differences between seals from East and West than between different sampling years. Higher proportions of PCBs and DDTs and lower proportions of chlordanes and HCHs were found in seals from East Greenland than in those from West Greenland. Based on principal component analysis of individual congener and compounds, seals from East Greenland were found to contain higher proportions of the higher chlorinated CB congeners. Varying patterns between sampling locations may be caused by different exposure situations related to contaminant emissions and transport, but different feeding habits may also affect the contaminant composition.     

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.     

Northern Rivers Ecosystem Initiative: Distribution and Effects of Contaminants

In response to a number of recommendations following the Northern Rivers Basin Studies (NRBS) contaminant program, the Northern Rivers Ecosystem Initiative (NREI) focused considerable attention on assessing contaminants from specific sources including pulp mill effluents, atmospheric transport of mercury and the Alberta oil sands operations. NRBS identified a number of major contaminants of concern including polychlorinated biphenyls, dioxins and furans, mercury and various hydrocarbons. Together, the NRBS and the NREI studies have demonstrated major declines in the levels of dioxins and furans over the last decade as pulp and paper mills have changed their process and treatment strategies in response to new Federal regulations. Polychlorinated biphenyls however, continue to be a concern for the region as their levels have not declined in fish and sediments over the course of these studies. Higher levels in sediments downstream of Grande Prairie and Hinton were identified, but the source of these contaminants remains unknown. Chlorinated pesticides were also investigated, and although toxaphene, DDT and other chlorinated organic pesticides were detected in fish tissue, they were present at very low levels. Studies on the oil sands industry in northern Alberta demonstrated limited impacts on the Athabasca River to date, although studies did identify slight to moderate impacts of natural oil seeps on fish and benthic communities in tributary streams. NREI studies also identified endocrine active compounds in the three pulp and paper mill effluents tested, but endocrine disruptive effects in wild fish were minimal. Municipal sewage effluents also contain endocrine active compounds and it is recommended that monitoring continue around these point sources.     

Levels and temporal trends of HCH isomers in ringed seals from West and East Greenland

Levels and temporal trends of the hexachlorocyclohexane isomers alpha-, beta- and gamma-HCH were analysed in blubber of juvenile ringed seals from West Greenland (1994 to 2006) and juvenile and adult ringed seals from East Greenland (1986 to 2006). No significant differences in the concentration levels in the juvenile seals were found between East and West Greenland for any of the three isomers. alpha-HCH concentrations were not significantly different between juvenile and adult ringed seals from East Greenland, whereas beta- and gamma-HCH concentrations were significantly higher in adult ringed seals. alpha- and beta-HCH in Greenland ringed seals were approximately a factor two lower than in the Canadian Arctic, and alpha-HCH was a factor 2-3 higher than in ringed seals from an area east of Svalbard, Norway. Annual decreases in ringed seals from Greenland during the study periods were detected to be 9.1-11.7%, 1.4-3.9% and 6.0-6.4% for alpha-, beta- and gamma-HCH, respectively, being quite similar in both East and West Greenland. Similar levels and trends in East and West Greenland support the general understanding of the pathways of HCH isomers to and in the Arctic.