Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

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.     

Global fate of POPs: current and future research directions

For legacy and emerging persistent organic pollutants (POPs), surprisingly little is still known in quantitative terms about their global sources and emissions. Atmospheric transport has been identified as the key global dispersal mechanism for most legacy POPs. In contrast, transport by ocean currents may prove to be the main transport route for many polar, emerging POPs. This is linked to the POPs' intrinsic physico-chemical properties, as exemplified by the different fate of hexachlorocyclohexanes in the Arctic. Similarly, our current understanding of POPs' global transport and fate remains sketchy. The importance of organic carbon and global temperature differences have been accepted as key drivers of POPs' global distribution. However, future research will need to understand the various biogeochemical and geophysical cycles under anthropogenic pressures to be able to understand and predict the global fate of POPs accurately.     

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.     

Trophic transfer of persistent organochlorine contaminants (OCs) within an Arctic marine food web from the southern Beaufort-Chukchi Seas

Stable isotope values (13C, 15N) and concentrations of persistent organochlorine contaminants (OCs) were determined to evaluate the near-shore marine trophic status of biota and biomagnification of OCs from the southern Beaufort-Chukchi Seas (1999-2000) near Barrow, AK. The biota examined included zooplankton (Calanus spp.), fish species such as arctic cod (Boreogadus saida), arctic char (Salvelinus alpinus), pink salmon (Oncorhynchus gorbuscha), and fourhorn sculpin (Myoxocephalus quadricornis), along with marine mammals, including bowhead whales (Balaena mysticetus), beluga whales (Delphinapterus leucas), ringed seals (Phoca hispida) and bearded seals (Erignathus barbatus). The isotopically derived trophic position of biota from the Beaufort-Chukchi Seas marine food web, avian fauna excluded, is similar to other coastal food webs in the Arctic. Concentrations of OCs in marine mammals were significantly greater than in fish and corresponded with determined trophic level. In general, OCs with the greatest food web magnification factors (FWMFs) were those either formed due to biotransformation (e.g. p,p'-DDE, oxychlordane) or considered recalcitrant (e.g. -HCH, 2,4,5-Cl substituted PCBs) in most biota, whereas concentrations of OCs that are considered to be readily eliminated (e.g. -HCH) did not correlate with trophic level. Differences in physical-chemical properties of OCs, feeding strategy and possible biotransformation were reflected in the variable biomagnification between fish and marine mammals. The FWMFs in the Beaufort-Chukchi Seas region were consistent with reported values in the Canadian Arctic and temperate food webs, but were statistically different than FWMFs from the Barents and White Seas, indicating that the spatial variability of OC contamination in top-level marine Arctic predators is attributed to differences in regional sources of contamination rather than trophic position.     

Geographical variation of persistent organochlorine concentrations in blubber of ringed seal (Phoca hispida) from the Canadian Arctic: univariate and multivariate approaches

Geographical variation of organochlorine (OC) concentrations in ringed seal (Phoca hispida) in the Canadian Arctic was studied using univariate and multivariate statistical techniques. The dataset consisted of 80 individual OC components (58 PCB congeners plus DDT- and chlordane (CHL)-related compounds, toxaphene, hexachlorocyclohexanes (HCH), chlorobenzenes (CBz), and dieldrin) determined in 221 ringed seal blubber samples from 13 locations throughout the Canadian Arctic from the period 1983 to 1989. Mean concentrations of the major OC groups in ringed seal blubber (SigmaPCBs, SigmaDDT, SigmaCHL and toxaphene), adjusted for the age and sex of the seals, showed few significant geographical differences. Principal components analysis was used to examine geographical trends. Significant differences in mean factor scores for three of four principal components were found between sampling locations. Locations in the western and high Arctic could be distinguished from those in Hudson Bay by highest scores along principal component two which was associated principally with CBz. PCB congeners with six or more chlorine substitutions declined with increasing north latitude, whereas more volatile OCs (CBz, HCH, less chlorinated PCBs) increased in the proportion of total OCs with latitude. Proportions of less chlorinated PCBs also decreased with increasing longitude, whereas slopes of regressions for more highly chlorinated PCBs increased significantly. The results were generally consistent with the 'cold condensation' hypothesis of increasing proportions of more volatile OCs with increasing latitude and distance from sources.     

Influence of overstory removal on growth of epiphytic mosses and lichens in western Oregon.

Will old-growth-associated epiphytes survive if the forest canopy is opened around them by thinning or partial harvest? If old-growth association is due to a species' environmental tolerances, it may not survive in the relatively open stands that result from such treatments. If, however, old-growth association is due to dispersal limitations rather than environmental tolerances, retention of host trees as refugia and sources of inoculum might carry populations of old-growth-associated epiphytes into young stands. We studied growth rates of lichen and moss transplants in a Douglas-fir (Pseudotsuga menziesii) forest (tree ages approximately 55 yr) in western Oregon for nine months before and 27 months after moderate thinning, creation of 0.4-ha patch cuts, and in control areas. We also assessed moss sporophyte production. We contrasted responses of one moss species, Isothecium myosuroides sensu lato, which is ubiquitous in forests of varying ages, with those of another moss, Antitrichia curtipendula, and a lichen, Lobaria oregana, which are both associated with old-growth forests. Both old-growth associates grew faster in thinned areas and patch cuts than in controls, while Isothecuim grew most slowly and produced fewest sporophytes in patch cuts. These species are likely to survive in remnants, assuming they can remain attached, and may be successful in young stands if they can disperse and establish there. Our results suggest that logging with green-tree retention and other silvicultural practices that preserve trees or shrubs hosting the species studied here are likely to encourage these species' development in managed forests.     

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.