Use of a vial equilibration technique to measure the change in fugacity capacity of avian food and feces samples for 1,2,3,4-tetrachlorobenzene.

A vial equilibration technique was used to estimate the fugacity capacities of food and feces samples for 1,2,3,4-tetrachlorobenzene (TCB). The method was calibrated using different volumes of n-octanol and by comparing the measured and predicted fugacity capacity (Zoct) of n-octanol for TCB. The vial equilibration technique showed linearity with increasing amounts of n-octanol added to the vial. However, the measured Zoct was on average 8.5 times lower than the literature estimate and interpreted to be influenced by co-solvent effects. The ratio of fugacity capacities of food/feces was 2.9 and was consistent with the ratio estimated using Zt calculation methods (4.3) which considers partitioning capacity of both lipids and non-lipid organic matter. These results provide experimental support to the use of lipid equivalent approaches as opposed to lipid normalization when estimating the partition capacity of biological samples containing low lipid contents.

Polychlorinated biphenyls: metabolic behavior of pure isomers in pigeons, rats, and brook trout.

The metabolic behavior of pure mono-, di-, tetra-, and hexachlorobiphenyl isomers in pigeons, rats, and brook trout was investigated. Excreta from these animals were extracted and examined by chromatographic and mass spectrometric techniques. The results showed conversion of the 4-chloro-, 4,4'-dichloro-, and 2,2',5,5'-tetrachlorobiphenyl isomers into monohydroxylated derivatives by the rat and pigeon whereas no hydroxymetabolites were detected in the excreta of the brook trout. No hydroxylated products of 2,2',4,4',5,5'-hexachlorobiphenyl were detected in the excreta of pigeons, rats, or brook trout.

Persistent organic pollutants and mercury in marine biota of the Canadian Arctic: an overview of spatial and temporal trends.

This review summarizes and synthesizes the significant amount of data which was generated on mercury (Hg) and persistent organic pollutants (POPs) in Canadian Arctic marine biota since the first Canadian Arctic Contaminants Assessment Report (CACAR) was published in 1997. This recent body of work has led to a better understanding of the current levels and spatial and temporal trends of contaminants in biota, including the marine food species that northern peoples traditionally consume. Compared to other circumpolar countries, concentrations of many organochlorines (OCs) in Canadian Arctic marine biota are generally lower than in the European Arctic and eastern Greenland but are higher than in Alaska, whereas Hg concentrations are substantially higher in Canada than elsewhere. Spatial coverage of OCs in ringed seals, beluga and seabirds remains a strength of the Arctic contaminant data set for Canada. Concentrations of OCs in marine mammals and seabirds remain fairly consistent across the Canadian Arctic although subtle differences from west to east and south to north are found in the proportions of various chemicals. The most significant development since 1997 is improvement in the temporal trend data sets, thanks to the use of archived tissue samples from the 1970s and 1980s, long-term studies using archeological material, as well as the continuation of sampling. These data cover a range of species and chemicals and also include retrospective studies on new chemicals such as polybrominated diphenyl ethers. There is solid evidence in a few species (beluga, polar bear, blue mussels) that Hg at some locations has significantly increased from pre-industrial times to the present; however, the temporal trends of Hg over the past 20-30 years are inconsistent. Some animal populations exhibited significant increases in Hg whereas others did not. Therefore, it is currently not possible to determine if anthropogenic Hg is generally increasing in Canadian Arctic biota. It is also not yet possible to evaluate whether the recent Hg increases observed in some biota may be due solely to increased anthropogenic inputs or are in part the product of environmental change, e.g., climate warming. Concentrations of most "legacy" OCs (PCBs, DDT, etc.) significantly declined in Canadian Arctic biota from the 1970s to the late 1990s, and today are generally less than half the levels of the 1970s, particularly in seabirds and ringed seals. Chlorobenzenes and endosulfan were among the few OCs to show increases during this period while summation operatorHCH remained relatively constant in most species. A suite of new-use chemicals previously unreported in Arctic biota (e.g., polybrominated diphenyl ethers (PBDEs), short chain chlorinated paraffins (SCCPs), polychlorinated naphthalenes (PCNs), perfluoro-octane sulfonic acid (PFOS) and perfluorocarboxylic acids (PFCAs)) has recently been found, but there is insufficient information to assess species differences, spatial patterns or food web dynamics for these compounds. Concentrations of these new chemicals are generally lower than legacy OCs, but there is concern because some are rapidly increasing in concentration (e.g., PBDEs), while others such as PFOS have unique toxicological properties, and some were not expected to be found in the Arctic because of their supposedly low potential for long-range transport. Continuing temporal monitoring of POPs and Hg in a variety of marine biota must be a priority.

Catalytic and immunologic characterization of hepatic and lung cytochromes P450 in the polar bear.

The Arctic Ocean is subject to considerable influx of anthropogenic pollutants including halogenated organic compounds. The polar bear (Ursus maritimus) is at the top of the arctic marine food web and is an ideal species for monitoring the level and distribution of contaminants in the arctic ecosystem. As the first step in the development of a biological method for assessing the functional exposure of polar bears to xenobiotics, biochemical studies were undertaken to characterize polar bear cytochromes P450. Liver and lung samples were obtained in the field from four, freshly killed, adult, male polar bears and immediately frozen at -196 degrees. Microsomes were subsequently prepared and used for the measurement of total cytochrome P450 content and aminopyrine N-demethylase, benzphetamine N-demethylase, ethylmorphine N-demethylase, p-nitrophenol hydroxylase and testosterone hydroxylase activities. Immunoblots containing hepatic and lung microsomal samples from the polar bears were probed using antibodies generated against several purified rat cytochrome P450 isozymes. Monoclonal antibody to rat cytochrome P450 1A1 and polyclonal antibodies to rat cytochromes P450 1A1, 2B1 and 3A1, as well as antibody to epoxide hydrolase, cross-reacted to varying degrees with polar bear hepatic microsomes. In addition, polyspecific antibody to the rat cytochrome P450 2C subfamily gave several immunostained protein bands, but antibodies specific to rat cytochrome P450 2C7 and 2C13 did not react, while antibody specific to cytochrome P450 2C11 yielded an ambiguous result. Except for anticytochrome P450 2B1 and polyspecific antibody to the cytochrome P450 2C subfamily, the antibodies listed above did not cross-react with polar bear lung microsomes at the protein concentrations used. The results demonstrate that polar bear liver contains multiple forms of cytochrome P450 that are catalytically active toward diverse substrates and that several of these forms are immunochemically related to rat cytochrome P450 isozymes. Immunochemical homologues of rat cytochrome P450 1A, 2B, 2C and 3A subfamilies, and of rat epoxide hydrolase are present in polar bear liver. In addition, the polar bears all had high levels of immunoreactive cytochrome P450 1A and 2B proteins, probably as a consequence of induction by environmental contaminants.

Analysis of hydroxylated metabolites of PCBs (OH-PCBs) and other chlorinated phenolic compounds in whole blood from Canadian inuit.

In this study, we identified the main hydroxylated polychlorinated biphenyls (OH-PCBs) and other chlorinated phenolic compounds and we determined their relative concentrations in whole blood from 13 male and 17 female Inuit from northern Quebec, Canada, and from a pooled whole blood sample from southern Quebec. We also determined concentrations of polychlorinated biphenyls (PCBs). Total OH-PCB concentrations were variable among the Inuit samples, ranging over 2 orders of magnitude (0.117-11.6 ng/g whole blood wet weight). These concentrations were equal to and up to 70 times those found for the southern Quebec pooled whole blood sample. Geometric mean concentrations of total OH-PCBs were 1.73 and 1.01 ng/g whole blood for Inuit men and women, respectively, and 0.161 ng/g whole blood for the southern population pool. There are limited data available for comparison, but the levels of OH-PCBs in Inuit are higher than those previously reported in the literature for other populations. There was a significant correlation (p < 0.005) between OH-PCBs and PCBs (r = 0.84) and both correlated significantly (p < 0.005) with age (r = 0.68 and 0.78, respectively). The ratio of OH-PCBs to PCBs was lower in Inuit (0.11) than in the southern Quebec pool (0.33). There is no apparent explanation for the difference. There was considerable variability in the congener pattern of the identified OH-PCBs. The main metabolite, 4-OH-CB109 (4-OH-2,3,3',4', 5-pentachlorobiphenyl), constituted 12-62% of the total OH-PCBs in the samples. Pentachlorophenol (PCP) was the dominant phenolic compound in blood, constituting 46% (geometric mean) of the total quantitated chlorinated phenolic compounds. PCP concentrations in Inuit blood ranged from 0.558 to 7.77 ng/g on a wet weight basis. All but two Inuit samples had lower concentrations than the southern Quebec pool (6.29 ng/g). The possible role of OH-PCBs in mediating PCB-induced adverse effects needs to be investigated further.

Inuit exposure to organochlorines through the aquatic food chain in arctic québec.

Inuit people (Eskimos) are likely exposed to persistent organochlorine compounds because their traditional diet includes fatty tissues of the arctic marine biota. Here we present the results of organochlorine compound analysis in milk fat samples from arctic Québec Inuit women and in fat tissues from various animal species inhabiting that region. The total concentration of polychlorinated biphenyl congeners in Inuit milk fat was similar to that of the beluga, while the profile of the 10 congeners resembled that of the polar bear. Mean concentrations of various organochlorines in milk-fat samples from Inuit women were between 2 and 10 times greater than those found in samples previously collected from southern Québec women. The Inuit mothers exhibit the greatest body burden known to occur from exposure to organochlorine residues present in the environment by virtue of their location at the highest trophic level of the arctic food web.

Geographical differences and time trends of persistent organic pollutants in the Arctic.

Geographical and temporal trends of total PCBs (SigmaPCBs) and hexachlorocyclohexanes (SigmaHCHs) have been examined in polar bear (Ursus maritimus) adipose tissue and ringed seal (Phoca hispida) blubber along a transect from Alaska to Svalbard and northern Norway/western Russia. PCB concentrations in polar bear show a strong west to east trend with higher levels in east Greenland, Svalbard. In ringed seal, highest PCB levels were found at two sites near the Russian coast. SigmaHCHs levels in ringed seals and polar bear show the reverse trend coinciding with much higher levels of SigmaHCHs in seawater in the North American Arctic. Some of these geographical differences may reflect dietary differences especially in the case of PCBs. Levels of SigmaPCBs in polar bears in the eastern Canadian Arctic appear to have increased from the 1970s to the 1980s but are now on the decline. SigmaPCBs and SigmaHCHs levels showed no significant change from the mid-1980s to 1990s in ringed seal blubber from three locations in the eastern Canadian Arctic.

Chlorinated hydrocarbon contaminants in arctic marine mammals.

By 1976, the presence of chlorinated hydrocarbon contaminants (CHCs) had been demonstrated in fur seal (Callorhinus ursinus), ringed seal (Phoca hispida), hooded seal (Cystophora cristata), bearded seal (Erignathus barbatus), walrus (Obdobenus rosmarus divergens), beluga (Delphinapterus leucas), porpoise (Phocoena phocoena) and polar bear (Ursus maritimus) in various parts of the Arctic. In spite of this early interest, very little subsequent research on contaminants in Arctic marine mammals was undertaken until the mid-1980s. Since that time, there has been an explosion of interest, resulting in a much expanded data base on contaminants in Arctic marine mammals. Except in the Russian Arctic, data have now been obtained on the temporospatial distribution of PCBs and other contaminants in ringed seal, beluga and polar bear. Contaminants in narwhal (Monodon monoceros) have also now been measured. On a fat weight basis, the sum of DDT-related compounds (S-DDT) and PCB levels are lowest in walrus (< 0.1 microgram/g), followed by ringed seal, (0.1-1 microgram/g range). Levels are an order of magnitude higher in beluga and narwhal (1-10 micrograms/g range). It appears that metabolism and excretion of S-DDT and PCBs may be less efficient in cetaceans, leading to greater biomagnification. Polar bears have similar levels of PCBs as cetaceans (1-10 micrograms/g), but with a much simpler congener pattern. DDE levels are lowest in polar bear, indicating rapid metabolism. Effects of age and sex on residue levels are found for all species where this was measured. Among cetaceans and ringed seal, sexually mature females have lower levels than males due to lactation. Although PCB levels in adult male polar bears are about twice as high as females, there is only a trivial age effect in either sex apart from an initial decrease from birth to sexual maturity (age 0-5). Comparison of levels of S-DDT and PCBs in Arctic beluga and ringed seal with those in beluga in the Gulf of St. Lawrence and ringed seal in the Baltic Sea, indicate that overall contamination of the Arctic marine ecosystem is 10-50 times less than the most highly contaminated areas in the northern hemisphere temperate latitude marine environment. Geographic distribution of residue levels in polar bears indicates a gradual increase from Alaska east to Svalbard, except PCB levels are significantly higher in eastern Greenland and Svalbard. Information on temporal trends is somewhat contradictory.(ABSTRACT TRUNCATED AT 400 WORDS)

Geographical distribution and identification of methyl sulphone PCB and DDE metabolites in pooled polar bear (Ursus maritimus) adipose tissue from western hemisphere arctic and subarctic regions.

The geographical distribution of methyl sulphone (MeSO2-) PCB and DDE metabolites is unknown for any species in any region. In this study, pooled male polar bear (Ursus maritimus) adipose samples from 12 arctic and subarctic regions from the Bering Sea to the Greenland Sea were analyzed for PCBs, DDE, and their MeSO2-metabolites. Each adipose pool contained from three to 27 lipid extracts prepared on an equal fat basis. The total (S-) MeSO2-PCB and MeSO2-DDE levels were generally higher in the east (Greenland) and south (Hudson Bay) and ranged from 138 to 633 ng/g lipid and 0.8-11 ng/g lipid, respectively. Five new MeSO2- compounds were identified and/or quantitated, 3M-DDE, 4M-CB64, 3M- and 4M-CB70, and 3M-CB149. The congeners 3M- and 4M-CB101 and 3M- and 4M-CB87 consistently accounted for ca. 50% of the S-MeSO2-PCBs. The MeSO2-PBC congener pattern was independent of geographic variation among the regions, implying that the pattern of atmospheric input and subsequent biomagnification of precursor PCBs is homogeneous in the western hemisphere. The ratio of S-MeSO2-PCBs to accumulating PCBs decreased very gradually (average value of .056 +/- .012) from west to east reflecting the proportion of higher chlorinated PCBs that are not major precursors of MeSO2-PCBs. The 3-MeSO2-DDE/DDE ratio fluctuated among regions with an average value of .033 +/- 0.017 [corrected].

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.

Body burdens and tissue concentrations of organochlorines in polar bears (Ursus maritimus) vary during seasonal fasts.

Lipophilic organochlorines (OCs) are ingested by mammals through their foods and are generally stored in adipose tissue depots. For some species, such as polar bears, the size of these depots can fluctuate seasonally by several-fold. However, the effect of these fluctuations on the fate of stored OCs in an animal with such labile lipid depots is unknown. We determined the whole body burden and tissue concentrations of OCs in free-ranging polar bears categorized by age (cubs-of-the-year, yearlings and adults) and sex before and after a fast averaging 56 days. Adipose tissue, plasma, and milk samples were analysed for sum of chlorobenzenes (sigma-ClBzs), hexachlorocyclohexanes (sigma-HCHs), chlordanes (sigma-CHLORs), dichlorodiphenyltrichloroethane compounds (sigma-DDTs) and polychlorinated biphenyls (sigma-PCBs). Decline in body mass during fasting ranged from 0.2 kg/day for cubs-of-the-year to 0.9 kg/day for sub-adult and adult males. Although all bears showed a decline in both lipid and lean mass during fasting, patterns of OC whole body burden changes were not consistent among compounds and bear classes. The burdens of sigma-DDTs declined by 11-50% for most bears during fasting, those of sigma-CHLORs declined by 67% during fasting in sub-adult and adult males but remained constant for all females, indicating male-specific metabolism of sigma-CHLORs. As fat depots became depleted, OC concentrations in the remaining adipose tissue varied; sigma-DDTs and sigma-HCHs declined while those of sigma-CHLORs and sigma-PCBs generally increased. Thus. within a 3-4 month fast, most polar bears were able to significantly rid their adipose tissue of sigma-DDTs and sigma-HCHs. Burdens of sigma-CHLORs (except males), sigma-ClBzs and sigma-PCBs remained constant for all classes of bears, therefore there was no significant excretion or metabolism during the fast of the specific congeners in these compound classes typically found in polar bears. The ratio of plasma/adipose tissue and milk/adipose tissue OC concentrations was the same for before and after the fast indicating that OC concentrations in polar bears are probably at a steady state among various body compartments. Concentrations of sigma-CHLORs and sigma-PCBs in milk almost doubled during the fast. As a consequence of this rise in milk OC concentrations, the whole body concentrations of these compounds increased in nursing cubs. Since developing young may be susceptible to the effects of environmental contaminants, the increased exposure of nursing cubs to OCs during a fast by their mothers is noteworthy.

Organochlorines and eggshell thinning in northern gannets (Sula bassanus) from Eastern Canada, 1968-1984.

The northern gannets (Sula bassanus) nesting on Bonaventure Island, Quebec, were studied from 1968 to 1984 in order to measure environmental contaminant levels and their relationship to productivity. Fresh eggs in 1969 contained a mean DDE level of 18.5 mg kg(-1) and had shells which were 17% thinner than pre-1947 samples. Unhatched eggs in 1969 had no outer calcified layer, a mean thickness 20% less than the pre-1947 mean, and mean DDE concentration of 30.6 mg kg(-1). Significantly higher levels of eight contaminants were measured in unhatched than in fresh eggs collected in 1969. DDE and shell thinning were also intercorrelated with nine other contaminants; these data strongly implicate toxic chemicals, particularly DDE, as the main cause for the low breeding success of Bonaventure gannets from 1966 to 1974. Extensive use of DDT to control forest insects around the Gulf of St Lawrence ceased in 1969. Use of DDT, dieldrin and PCBs was restricted in North America during the early 1970s. Residues of DDT, DDD, DDE, PCBs, dieldrin, HCB and chlordane-related compounds in gannet eggs decreased significantly during this study. Heptachlor epoxide remained constant while alpha-HCH appeared to increase. Estimated half-lives ranged from 3.1 years for DDD to 35.4 years for oxychlordane. The breeding success and population of the colony have coincidentally increased.

Heavy metals and essential elements in livers of the polar bear (Ursus maritimus) in the Canadian Arctic.

Polar bear (Ursus maritimus) livers (67) from six Management Zones in the western and central Canadian Arctic were analysed for 22 elements. Several, Ba, Be, Co, Mo, Ti, V and Zr, were near the detection limit in all cases. Baseline data were obtained for the remaining elements, Ag, As, Ca, Cd, Cu, Fe, Hg, K, Mg, Mn, Na, P, Se, Sr and Zn. No statistically significant effect of age, sex or geographical location was found for any of the elements, except Cd, Hg and Se, for which age and geographical location effects were found. The frequency distribution of Zn levels was bimodal. The second peak in the distribution appeared to be related to elevated levels of Cu. The average level of Cu was 104 mg kg-1 (dry wt.), higher than other marine mammals. Average levels of Cd were significantly higher in the eastern zones, but were always less than 1.0 mg kg-1 (dry wt.), significantly lower than their prey species. This may be due to the preference of polar bears for eating seal skin and fat which is low in Cd. Mercury levels tended to be higher in the western zones bordering the Beaufort Sea, which may be related to a higher proportion of bearded seal in their diet. Mean Hg levels ranged from 20 mg kg-1 in the eastern zones were related to age by the expression: Hg (mg kg-1 dry wt.) = 15.7 + 8.0 Age (years). Mercury levels in the most northerly zone near Melville Island were very high: Hg (mg kg-1 dry wt.) = 18.4 + 27.5 Age (years). Levels of Hg and Se were very highly correlated, with a molar ratio of 1.27:1, Hg/Se.

Arctic terrestrial ecosystem contamination.

Limited data have been collected on the presence of contaminants in the Arctic terrestrial ecosystem, with the exception of radioactive fallout from atmospheric weapons testing. Although southern and temperate biological systems have largely cleansed themselves of radioactive fallout deposited during the 1950s and 1960s, Arctic environments have not. Lichens accumulate radioactivity more than many other plants because of their large surface area and long life span; the presence and persistence of radioisotopes in the Arctic is of concern because of the lichen----reindeer----human ecosystem. Effective biological half-life of cesium 137 is reckoned to be substantially less than its physical half-life. The database on organochlorines in Canadian Arctic terrestrial mammals and birds is very limited, but indications are that the air/plant/animal contaminant pathway is the major route of these compounds into the terrestrial food chain. For terrestrial herbivores, the most abundant organochlorine is usually hexachlorobenzene followed by hexachlorocyclohexane isomers. PCB accumulation favours the hexachlorobiphenyl, pentachlorobiphenyl and heptachlorobiphenyl homologous series. The concentrations of the various classes of organochlorine compounds are substantially lower in terrestrial herbivore tissues than in marine mammal tissues. PCBs and DDT are the most abundant residues in peregrine falcons (a terrestrial carnivore) reaching average levels of 9.2 and 10.4 micrograms.g-1, respectively, more than 10 times higher than other organochlorines and higher than in marine mammals, including the polar bear. Contaminants from local sources include metals from mining activities, hydrocarbons and waste drilling fluids from oil and gas exploration and production, wastes from DEW line sites, naturally occurring radionuclides associated with uranium mineralization, and smoke containing SO2 and H2SO4 aerosol from the Smoking Hills at Cape Bathurst, N.W.T.

Total organically-bound chlorine and bromine in Lake Ontario herring gull eggs, 1977, by instrumental neutron activation and chromatographic methods.

In order to determine the extent to which organically-bound chlorine in Herring Gull eggs from Lake Ontario can be accounted for by gas chromatographic analysis, comparison was made with values obtained for total chlorine using instrumental neutron activation analysis (INAA). Total chlorine and bromine (mg/kg fresh weight of egg) was determined by INAA on crude extract (Cl, 65 +/- 35; Br, 1.03 +/- 1.00), Florisil-chromatography treated extracts (Cl, 46 +/- 10; Br, 0.93 +/- 0.82) and H2SO4-treated extracts (Cl, 43 +/- 11; Br, 0.44 +/- 0.22) of eggs collected from seven colonies around Lake Ontario in 1977. Levels of chlorine were also determined by gas chromatography using the Hall electrolytic conductivity detector (51 +/- 11 mg/kg) and estimated by conversion of levels of individual residues determined by electron-capture gas chromatography (61 +/- 12 mg/kg). The agreement between the various determinations indicated that PCBs, DDE, mirex and photomirex accounted for most of the organically-bound chlorine. Two colonies had total chlorine levels in crude extracts 2--4 times higher than could be accounted for by know compounds. The "excess" chlorine was removed by H2SO4-treatment or Florisil clean-up. The same two samples had abnormally high bromine levels, possibly indicating the presence of compounds formed during aqueous chlorination processes.

Preliminary results of fasting on the kinetics of organochlorines in polar bears (Ursus maritimus).

We determined concentrations of polychlorinated biphenyls (PCBs), chlordanes (CHLORs), chlorobenzenes (CBzs), hexachlorocyclohexanes (HCHs), and dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDD and DDE) in the tissues of individual polar bears (Ursus maritimus) before and after a lengthy period of fasting. Polar bears are an ideal model for such studies. They undergo one of the most extreme fasts known for any mammal and are located at the top of a long food chain, thus biomagnification of organochlorines (OC) is significant. Adipose tissue and milk were collected from different reproductive classes of adult females (solitary/pregnant, with cubs-of-the-year, with yearling cubs) and were analyzed for organochlorine content. As the fasting period progressed and adipose reserves decreased, concentrations of some organochlorines in the adipose tissue and milk increased on a lipid weight basis. The transfer of contaminants from mothers to offspring thus also increases with duration of the fasting period. This phenomenon could adversely influence the survival and growth of cubs during the critical early phase of their development.

Geographical distribution of metals in livers of polar bears from the Northwest Territories, Canada.

Levels of Ag, Ca, Cd, cu, Fe, Hg, K, Mg, Mn, Na, P, Se and Zn were determined in livers of polar bears collected in 1984 in six zones in the Lancaster Sound. Baffin Bay and Hudson Bay areas of the Northwest Territories of Canada and compared with data collected in 1982 for the western part of the Canadian Arctic. Only levels of Cu, K and Zn were found to have no statistically significant differences among zones. The lowest levels of Ca, Fe, Mg, Mn, Na and P were found in the western Arctic, but geographical differences were probably inconsequential. Cadmium levels were significantly lower in the western Arctic zones than in the other areas, and reverse was true for levels of Hg and Se. Levels of Cd, Hg and Se in polar bear liver were positively correlated with age, whereas K, Mn, Mg and P were negatively correlated with age. Iron was significantly higher in females than males. Rates of accumulation of Cd with age were 2 3 times lower in polar bears from zones west of approximately 95 degrees W than the other areas, whereas Hg and Se rates of accumulation were about 7 and 10 times higher in bears from the zones near the Beaufort Sea than from Hudson Bay. The Hg/Se molar ratios averaged 1.10 +/- 0.19 for most of the surveyed zones excluding Hudson Bay, where the average ratio was almost two-fold higher (2.13 +/- 1.58). It is probable that natural variation in Hg levels in the marine environment due to geological or atmospheric deposition factors, and differences in polar bear feeding ecology among zones, account for the differences in the geographical distribution of Hg. The distribution of Cd is more likely to be related to differences in feeding ecology of the bear's principal prey, the ringed seal.

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.

Bald eagle mortality and chlorinated hydrocarbon contaminants in livers from British Columbia, Canada, 1989-1994.

Between 1989 and 1994, we obtained 278 carcasses of bald eagles (Haliaeetus leucocephalus) found dead or dying in British Columbia, Canada. All specimens were necropsied and the cause of death determined wherever possible. Livers from a subset of 75 birds were analyzed for polychlorinated biphenyl (PCB) and organochlorine (OC) pesticide residues. A further subset of 19 eagles found dead around the Strait of Georgia, an area of known pulp mill pollution, in summer, and therefore presumably resident birds, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and non-ortho PCBs. Liver concentrations ranged from less than 1 to 190 mg/kg for DDE, and up to 72 mg/kg for total PCBs. Concentrations of other OCs were generally less than 1 mg/kg, with the exception of chlordane-related compounds which were occasionally over 2 mg/kg. All birds analyzed for PCDDs and PCDFs contained detectable concentrations of the major 2,3,7,8-substituted isomers. Some birds were very contaminated; one eagle found near a kraft pulp mill site in 1990 contained: 400 ng/kg 2,3,7,8-TCDD, 1400 ng/kg 1,2,3,7,8-PnCDD and 4400 ng/kg 1,2,3,6,7,8-HxCDD. Birds with higher PCB and dichlorodiphenyldichloroethane (DDE) concentrations appeared to weigh less, and there was a significant negative relationship between both PCBs and DDE and numeric scoring of body condition, reflecting the well known process of starvation-induced mobilization of body lipids and contaminants. Birds with higher 2,3,7,8-TCDD concentrations tended to have unusually low concentrations of 2,3,7,8-TCDF, interpreted to indicate hepatic cytochrome P4501A-type induction by TCDD and subsequent metabolism of TCDF.

Chlordane components and metabolites in seven species of Arctic seabirds from the Northwater Polynya: relationships with stable isotopes of nitrogen and enantiomeric fractions of chiral components.

The Northwater Polynya (NOW) is a large area of year-round open water found in the high Arctic between Ellesmere Island and Greenland. NOW has high biological productivity compared with other arctic marine areas, and supports large populations of several seabird species. Seven species of seabirds, dovekie (Alle alle, DOVE), thick-billed murre (Uria lomvia, TBMU), black guillemot (Cepphus grylle, BLGU), black-legged kittiwake (Rissa tridactyla, BLKI), ivory gull (Pagophila eburnea, IVGU), glaucous gull (Larus hyperboreus, GLGU) and northern fulmar (Fulmaris glacialis, NOFU) were collected in May and June 1998 to determine chlordane concentrations in liver and fat and to examine species differences, relationships with stable isotopes of nitrogen, and enantiomeric fractions (EFs) of chiral components. sigma CHLOR concentrations varied over an order of magnitude among species, from a low of 176 +/- 19 ng/g (lipid corrected) in TMBU liver to a high of 3190 +/- 656 ng/g (lipid corrected) in NOFU liver. Lipid-corrected concentrations of chlordane did not vary between sex for any species or between fat and liver except for the DOVE, that had fat concentrations that were significantly greater than the liver. delta 15N values described a significant percentage of the variability of concentrations for most chlordane components, although less than what has been reported for whole food chains. Slopes of delta 15N versus concentration of chlordane components and sigma CHLOR were similar with the exception of those which were metabolized (trans-chlordane) or formed through biotransformation (oxychlordane). The relative proportions of chlordane components in seabirds were related to phylogeny; the procellariid (NOFU) had the greatest percentage of oxychlordane (> 70%), followed by the larids (BLKI, IVGU and GLGU; 40-50%) and the alcids (DOVE and BLGU; 10-20%). The exception was TBMU, an alcid, where oxychlordane made up > 40% of its chlordane. EFs of chiral components failed to predict concentration or trophic level, but did identify biotransformation differences between species and chlordane components. TBMU appeared to have a greater capacity to metabolize and eliminate chlordane, based on high proportions of oxychlordane, the highest EFs for oxychlordane and heptachlor epoxide, and a delta 15N-sigma CHLOR value which was well below the relationships developed for all seabird species.