Derek C.G. Muir

Contaminants in the Canadian Arctic: 5 years of progress in understanding sources, occurrence and pathways

Recent studies of contaminants under the Canadian Northern Contaminants Program (NCP) have substantially enhanced our understanding of the pathways by which contaminants enter Canadas Arctic and move through terrestrial and marine ecosystems there. Building on a previous review (Barrie et al., Arctic contaminants: sources, occurrence and pathways. Sci Total Environ 1992:1-74), we highlight new knowledge developed under the NCP on the sources, occurrence and pathways of contaminants (organochlorines, Hg, Pb and Cd, PAHs, artificial radionuclides). Starting from the global scale, we examine emission histories and sources for selected contaminants focussing especially on the organochlorines. Physical and chemical properties, transport processes in the environment (e.g. winds, currents, partitioning), and models are then used to identify, understand and illustrate the connection between the contaminant sources in industrial and agricultural regions to the south and the eventual arrival of contaminants in remote regions of the Arctic. Within the Arctic, we examine how contaminants impinge on marine and terrestrial pathways and how they are subsequently either removed to sinks or remain where they can enter the biosphere. As a way to focus this synthesis on key concerns of northern residents, a number of special topics are examined including: a mass balance for HCH and toxaphene (CHBs) in the Arctic Ocean; a comparison of PCB sources within Canadas Arctic (Dew Line Sites) with PCBs imported through long-range transport; an evaluation of concerns posed by three priority metals--Hg, Pb and Cd; an evaluation of the risks from artificial radionuclides in the ocean; a review of what is known about new-generation pesticides that are replacing the organochlorines; and a comparison of natural vs. anthropogenic sources of PAH in the Arctic. The research and syntheses provide compelling evidence for close connectivity between the global emission of contaminants from industrial and agricultural activities and the Arctic. For semi-volatile compounds that partition strongly into cold water (e.g. HCH) we have seen an inevitable loading of Arctic aquatic reservoirs. Drastic HCH emission reductions have been rapidly followed by reduced atmospheric burdens with the result that the major reservoir and transport agent has become the ocean. In the Arctic, it will take decades for the upper ocean to clear itself of HCH. For compounds that partition strongly onto particles, and for which the soil reservoir is most important (e.g. PCBs), we have seen a delay in their arrival in the Arctic and some fractionation toward more volatile compounds (e.g. lower-chlorinated PCBs). Despite banning the production of PCB in the 1970s, and despite decreases of PCBs in environmental compartments in temperate regions, the Arctic presently shows little evidence of reduced PCB loadings. We anticipate a delay in PCB reductions in the Arctic and environmental lifetimes measured in decades. Although artificial radionuclides have caused great concern due to their direct disposal on Russian Shelves, they are found to pose little threat to Canadian waters and, indeed, much of the radionuclide inventory can be explained as remnant global fallout, which was sharply curtailed in the 1960s, and waste emissions released under license by the European reprocessing plants. Although Cd poses a human dietary concern both for terrestrial and marine mammals, we find little evidence that Cd in marine systems has been impacted by human activities. There is evidence of contaminant Pb in the Arctic, but loadings appear presently to be decreasing due to source controls (e.g. removal of Pb from gasoline) in Europe and North America. Of the metals, Hg provokes the greatest concern; loadings appear to be increasing in the Arctic due to global human activities, but such loadings are not evenly distributed nor are the pathways by which they enter and move within the Arctic well understood.

Arctic contaminants: sources, occurrence and pathways

Potentially toxic organic compounds, acids, metals and radionuclides in the northern polar region are a matter of concern as it becomes evident that long-range transport of pollution on hemispheric to global scales is damaging this part of the world. In this review and assessment of sources, occurrence, history and pathways of these substances in the north, the state of knowledge of the transport media--the ocean and atmospheric circulation--is also examined. A five-compartment model of the northern region is developed with the intent of assessing the pathways of northern contaminants. It shows that we know most about pathways of acids, metals and radionuclides and least about those of complex synthetic organic compounds. Of the total annual inputs of anthropogenic acidic sulphur and the metals lead and cadmium to the Arctic via the atmosphere, an estimated 10-14% are deposited. A water mass budget for the surface layer of the Arctic Ocean, the most biologically active part of that sea, is constructed to examine the mass budget for one of the major persistent organochlorine compound groups found in remote regions, hexachlorocyclohexanes (HCH), one isomer of which is lindane. It is concluded that both the atmosphere and the ocean are important transport media. Even for the HCH substances which are relatively easily measured and simple in composition compared to other synthetic organics, we know little about the occurrence and environmental physical/chemical characteristics that determine pathways into the food chain. More environmental measurements, chemical characterization studies and environmental chemical transport modelling are needed, as is better knowledge of the circulation of the Arctic Ocean and the marine food web.

Arctic marine ecosystem contamination

The current state of knowledge of levels, spatial and temporal trends of contaminants in the Arctic marine ecosystem varies greatly among pollutants and among environmental compartments. Levels of polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and some heavy metals such as mercury and lead, in Arctic marine mammals and fish are relatively well documented because of the need for comparisons with biota in more polluted environments and interest in the contamination of native diets. Levels of heavy metals, alkanes, polyaromatic hydrocarbons (PAH) and OCs in the Arctic Ocean are comparable to uncontaminated ocean waters in the mid-latitudes. But concentrations of alpha- and gamma-hexachlorocyclohexane (HCHs) are higher in northern waters far removed from local sources, possibly because lower water temperature reduces transfer to the atmosphere. Bioaccumulation of OCs and heavy metals in Arctic marine food chains begins with epontic ice algae or phytoplankton in surface waters. Polychlorinated camphenes (PCC), PCBs, DDT- and chlordane-related compounds are the major OCs in marine fish, mammals and seabirds. Mean concentrations of most PCBs and OC pesticides in ringed seal (Phoca hispida) and polar bear (Ursus maritimus) populations in the Canadian Arctic are quite similar indicating a uniform geographic distribution of contamination, although alpha-HCH showed a distinct latitudinal gradient in bears due to higher levels in zones influenced by continental runoff. Ringed seals from Spitzbergen have higher levels of PCBs, total DDT and polychlorinated dioxins/furans (PCDD/PCDFs). In contrast to other OCs, PCDD/PCDFs in Canadian Arctic ringed seals and polar bears were higher in the east/central Arctic than at more southerly locations. Remarkably high cadmium levels are found in kidney and liver of narwhal (Monodons monoceros) from western Baffin Bay (mean of 63.5 micrograms g-1) and western Greenland waters (median of 39.5 micrograms g-1). Mercury concentrations in muscle of ringed seal and cetaceans frequently exceed 0.5 microgram g-1 especially in older animals. Cadmium concentrations in polar bear liver increased from west to east, while mercury levels were higher in ringed seals from the western Canadian Arctic, which suggests that natural sources of these metals predominate. Studies of temporal trends in OCs in ringed seals and seabirds in the Canadian Arctic indicate PCB and DDT levels declined significantly from the early 1970s to the 1980s. There is a lack of temporal trend data for other OC pesticides as well as for heavy metals and hydrocarbons.(ABSTRACT TRUNCATED AT 400 WORDS)

Spatial and temporal trends and effects of contaminants in the Canadian Arctic marine ecosystem: a review

Recent studies have added substantially to our knowledge of spatial and temporal trends of persistent organic pollutants and heavy metals in the Canadian Arctic marine ecosystem. This paper reviews the current state of knowledge of contaminants in marine biota in the Canadian Arctic and where possible, discusses biological effects. The geographic coverage of information on contaminants such as persistent organochlorines (OCs) (PCBs, DDT- and chlordane-related compounds, hexachlorocyclohexanes, toxaphene) and heavy metals (mercury, selenium, cadmium, lead) in tissues of marine mammal and sea birds is relatively complete. All major beluga, ringed seal and polar bear stocks along with several major sea bird colonies have been sampled and analysed for OC and heavy metal contaminants. Studies on contaminants in walrus are limited to Foxe Basin and northern Québec stocks, while migratory harp seals have only been studied recently at one location. Contaminant measurements in bearded seal, harbour seal, bowhead whale and killer whale tissues from the Canadian Arctic are very limited or non-existent. Many of the temporal trend data for contaminants in Canadian Arctic biota are confounded by changes in analytical methodology, as well as by variability due to age/size, or to dietary and population shifts. Despite this, studies of OCs in ringed seal blubber at Holman Island and in sea birds at Prince Leopold Island in Lancaster Sound show declining concentrations of PCBs and DDT-related compounds from the 1970s to 1980s then a levelling off during the 1980s and early 1990s. For other OCs, such as chlordane, HCH and toxaphene, limited data for the 1980s to early 1990s suggests few significant declines in concentrations in marine mammals or sea birds. Temporal trend studies of heavy metals in ringed seals and beluga found higher mean concentrations of mercury in more recent (1993/1994) samples than in earlier collections (1981-1984 in eastern Arctic, 1972-1973 in western Arctic) for both species. Rates of accumulation of mercury are also higher in present day animals than 10-20 years ago. Cadmium concentrations in the same animals (eastern Arctic only) showed no change over a 10-year period. No temporal trend data are available for metals in sea birds or polar bears. There have been major advances in knowledge of specific biomarkers in Canadian Arctic biota over the past few years. The species with the most significant risk of exposure to PCBs and OC pesticides may be the polar bear which, based on comparison with EROD activity in other marine mammals (beluga, ringed seal), appears to have elevated CYP1A-mediated activity. The MFO enzyme data for polar bear, beluga and seals suggest that even the relatively low levels of contaminants present in Arctic animals may not be without biological effects, especially during years of poor feeding.

Biological and chemical factors of importance in the bioaccumulation and trophic transfer of persistent organochlorine contaminants in arctic marine food webs

Recent studies of arctic marine food webs have provided detailed insights regarding the biological and chemical factors that influence the bioaccumulation and trophic transfer of persistent organochlorine (OC) contaminants in aquatic systems. The present paper summarizes the recent literature with an emphasis on identifying important ecological factors for explaining variability of OC concentrations among organisms. The Arctic ecosystem has a number of unique attributes, including long food chains, reduced diversity of species, similar food webs across the entire region, and limited influence from pollution point sources. Lipid content, body size, age, gender, reproduction, habitat use, migration, biotransformation, seasonal changes in habitat conditions, feeding ecology, and trophic position have all been demonstrated to influence OC concentrations and bioaccumulation in arctic marine biota. The relative importance of each factor varies among OCs and organisms. Diet or trophic level is the dominant factor influencing OC concentrations and dynamics in seabirds and marine mammals, although biotransformation can significantly influence nonrecalcitrant OCs, such as hexachlorocyclohexane isomers. Dietary accumulation of OCs is also an important route of exposure for arctic fish and zooplankton, and biomagnification of OCs may also occur among these organisms. To date, only limited attempts have been made to model trophic transfer of OCs in the arctic marine food web. Although models developed to assess OC dynamics in aquatic food webs have included some biological variables (e.g., lipid content, feeding rate, diet composition, and growth rate), selection of processes included in these models as well as their mathematical solutions and parameterization all introduce simplification. This reduces biological validity of the models and may be particularly problematic in a highly seasonal environment, such as the Arctic Ocean.

Multi-year observations of organohalogen pesticides in the Arctic atmosphere

Atmospheric measurements of organohalogen pesticides (OCs) have been made in both the Canadian and Russian Arctic. A full quality-controlled database of weekly samples is now available for the years 1992–94. Hexachlorobenzene (HCB) and the hexachlorocyclohexanes (HCHs) were the most predominant compounds in the atmosphere, followed by the chlordanes and endosulfan. Evidence of a seasonality in air concentrations was apparent particularly for the pesticide metabolites, compounds such as oxychlordane, heptachlor epoxide and dieldrin showing a significant positive correlation with temperature (p<0.01). An exception to this was p, p′-DDE which showed elevated levels during the winter. Large spatial differences in mean annual concentrations of most OCs were not evident; however, spatial differences were apparent in α/γ-HCH ratios between the high Arctic site of Alert and the Yukon site of Tagish. The influence of both the European sector and the regional effect of the Arctic Ocean on the high Arctic probably accounted for this difference. A decline in the trans-chlordane/cis-chlordane ratio compared to studies during the 1980s may indicate a more weathered source of chlordane to be present in the Arctic by the mid-1990s. Slopes generated from plots of partial pressure (ln P) versus 1/T for selected compounds were considerably less steep than those derived from temperate studies. It is inferred here that long-range transport has a large influence on contaminant levels in the arctic atmosphere.

Bioaccumulation of organochlorines through a remote freshwater food web in the Canadian Arctic

Abstract Persistent organochlorines (OCs) were measured in water, sediment and biota from a remote lake in the Canadian Arctic to examine the bioaccumulation of atmospherically deposited OCs through a high-latitude freshwater food web. All major OC groups (polychlorinated biphenyls [PCBs], dichlorodiphenyl trichloroethane and metabolites [DDT], chlordane [CHL]-related compounds, and hexachlorocyclohexane [HCH] isomers) were detectable at sub-ng liter −1 concentrations in lake water and at low ng g −1 levels (dry wt) in surface sediments. Estimates of air–water exchange using a two-film model suggested that lake waters were close to equilibrium with the atmosphere for αHCH, trans -nonachlor and p,p ′-DDE but that PCB congeners 52 and 153 were undergoing volatilization. Despite the relatively short open water season, gas absorption was found to be a major input pathway into the lake, when compared to estimated inputs from precipitation. Mean concentrations of ΣHCH, ΣDDT, ΣCHL and ΣPCB ranged from 1 to 10 ng g −1 wet wt in arctic char and from 2 to 82 ng g −1 in lake trout and were comparable to results from other lakes in the Canadian Arctic. Exceptionally high concentrations (six- to 10-fold higher than mean values) of these OCs were observed in a few lake trout and were explained by the larger size, longer lifespans and higher lipid contents of these individuals. Trophic interrelationships of food-web organisms were characterized using their tissue stable carbon and nitrogen isotope ratios. Through the food web, lipid-adjusted concentrations of αHCH, trans -nonachlor, p,p ′-DDE, and PCB congeners 52 and 153 in biota were significantly related to their trophic position as determined by measurements of tissue stable nitrogen isotope ratios. In addition, the slopes and coefficients of determination for these relations increased with the lipophilicity and recalcitrance of the OCs, demonstrating that the more lipophilic OCs bioaccumulated to a greater degree through this food web even after accounting for the effects of lipid.

Empirical and modeling evidence of regional atmospheric transport of current-use pesticides.

Water samples from 30 lakes in Canada and the northeastern United States were analyzed for the occurrence of 27 current-use pesticides (CUPs). Eleven CUPs were frequently detected in lakes receiving agricultural inputs as well as in remote lakes hundreds of kilometers from known application areas. These included the triazine herbicide atrazine and its desethylated degradation product; the herbicides alachlor, metolachlor, and dacthal; the organophosphate insecticides chlorpyrifos, diazinon, and disulfoton; the organochlorine insecticides alpha-endosulfan and lindane; and the fungicides chlorothalonil and flutriafol. For six of the pesticides, empirical half-distances on the order of 560 to 1,820 km were estimated from the water-concentration gradient with latitude. For most of the pesticides, a suite of assessment models failed to predict such atmospheric long-range transport behavior, unless the effect of periods of lower hydroxyl radical concentrations and dry weather were taken into account. Observations and model results suggest that under the conditions prevailing in south-central Canada (relatively high latitude, low precipitation rates), many CUPs will be able to undergo regional-scale atmospheric transport and reach lakes outside areas of agricultural application. When assessing the potential of fairly reactive and water-soluble substances to undergo long-range transport, it is imperative to account for periods of no precipitation, to assure that degradation rate constants are correct, and to apply oxidant concentrations that are valid for the region and time period of interest.

The fate and persistence of trifluoroacetic and chloroacetic acids in pond waters

The environmental fate of trichloro-, dichloro-, and monochloroacetic acids, and trifluoroacetic acid was investigated using field aquatic microcosms and laboratory sediment-water systems. Trifluoroacetic acid was extremely persistent and showed no degradation during a one-year field study, though it appeared to undergo transient partitioning within an unknown pond phase as the temperature of the surroundings was reduced. Of the three chloroacetic acids, trichloro had the longest residence time (induction and decay) (approximately 40 d), dichloro the shortest (approximately 4 d), and monochloro an intermediate residence time (approximately 14 d). Laboratory studies suggest that the biodegradation of trichloro-, dichloro-, and monochloroacetic acids leads primarily to the formation of chloride and oxalic, glyoxalic, and glycolic acids, respectively.

Are organohalogen contaminants a cofactor in the development of renal lesions in East Greenland polar bears (Ursus maritimus)

Tissues of polar bears (Ursus maritimus) from East Greenland contain the highest concentrations of organohalogen contaminants (OHCs) among subpopulations of any mammalian species in the Arctic. Negative associations also have been found between OHC concentrations and bone mineral density and liver histology parameters for this subpopulation of polar bears. The present study examined the OHC concentrations and adverse effects on renal tissue for 75 polar bears collected during 1999 to 2002. Specific lesions were diffuse glomerular capillary wall thickening, mesangial glomerular deposits, tubular epithelial cell hyperplasia, hyalinization of the tubular basement membrane, tubular dilatation, atrophy and necrosis, tubular medullary hyalin casts, interstitial fibrosis, and mononuclear cell infiltration. With the exception of mononuclear cell infiltrations, all these parameters were correlated with age, whereas none was associated with the sex of the animals. In an age-controlled statistical analysis of covariance, increases in glomerular mesangial deposits and interstitial fibrosis were significantly (p < 0.05) correlated with polybrominated diphenyl ether (sigmaPBDE) concentrations in subadults. In adult males, statistically significant (p < 0.05) positive correlations were found for tubular epithelial cell hyperplasia and dieldrin concentration; diffuse glomerular capillary wall thickening and chlordane (sigmaCHL) concentrations, and tubular medullary hyalin casts and sigmaCHL, sigmaPBDE, polychlorinated biphenyl, and hexachlorocyclohexane concentrations. The lesions were consistent with those reported previously in highly OHC-contaminated Baltic seal populations and exposed laboratory animals. The renal lesions were a result of aging. However, based on the above statistical findings as well as the nature of the findings, we suggest that long-term exposure to OHCs may be a cofactor in renal lesion occurrence, although other cofactors, such as exposure to heavy metals and recurrent infections from microorganisms, cannot be ruled out. This is new and important knowledge in the assessment of health status among wildlife populations and humans relying on food resources that are contaminated with OHCs.