Accumulation, metabolism, and food-chain transfer of chlorinated and brominated contaminants in subadult white whales (Delphinapterus leucas) and narwhals (Monodon monoceros) from Svalbard, Norway.

The concentrations and patterns of polychlorinated biphenyls (PCBs), chlorinated pesticides, and polybrominated diphenyl ethers (PBDEs) were studied in white whales (Delphinapterus leucas) and narwhals (Monodon monoceros) from Svalbard, Norway. In addition, their main food items were included in the study. In the whales, a broad range of pollutants was found in relatively high concentrations. PCBs and pesticides were approximately 3000 and 8000 ng/g lipid, respectively, for white whales and three times higher for narwhals. PBDEs 47 were approximately 70 ng/g lipid for white whales and 170 ng/g lipid for narwhals. Compared with other marine mammals from the same area, contaminant levels are among the highest levels ever measured. These high levels are likely in part because of a decreased capacity to metabolize contaminants. Metabolic indices indicated that most compounds accumulate to the same degree in white whales and narwhals, but for some toxaphenes and chlordanes, narwhals might have a decreased metabolism and consequently a higher accumulation. The three-times-higher contaminant levels in blubber of narwhals was further explained by substantially higher contaminant levels in their more benthic diet. The high levels and broad pattern of accumulating pollutants make white whales and narwhals excellent indicators for a wide range of contaminants in the Arctic.

The importance of diet on exposure to and effects of persistent organic pollutants on human health in the Arctic.

AIM: To describe the importance of diet on exposure to and possible health effects of persistent organic pollutants (POPs) in the Arctic. METHODS: The study is based on a literature review. RESULTS: Minor decreases in POPs and minor increases in Hg levels in Arctic populations in Greenland, Eastern Russia, Western Alaska and Eastern Canada are likely to occur by the year 2010 and major decreases in both POPs and Hg levels in these same populations by 2030. Levels of POPs and metals in populations in the Faeroe Islands and the Scandinavian countries are already reasonably low and are only likely to decline marginally by 2030. Estimating the effects on the basis of current knowledge is difficult, but the combination of improved methodology and selection of risk groups will be a progressive step in the process. Any strategies based on traditional food substitution should ensure that the value of the dietary components is sustained. CONCLUSIONS: To improve our understanding of the health effects associated with exposure to contaminants in the Arctic, we recommend that circumpolar epidemiological studies should be implemented on a larger scale. MeHg- and POPs-related effects are still the key issues. However, the role of newly discovered contaminants, such as PBDEs (polybrominated diphenyl ethers) and PCNs (polychlorinated naphthalenes), should be investigated. For exposure assessment, mixtures and nutritional interactions should be considered in epidemiological studies. Epidemiological studies on nutritional benefits of traditional foods should be incorporated in risk-assessment profiles. We need a more nuanced view on human dietary exposure to xenobiotics. Risk should not be evaluated alone, but seen in relation to benefits from specific diets. It is essential that countries ratify and implement multinational environmental agreements.

Sources and transport of persistent pollutants to the Arctic.

During the last two decades the importance of long-range transport as a contaminant source for the pristine Arctic regions has been proven. Models are developed in order to predict spatial, seasonal and structural dependent patterns in the distribution of antropogenic pollutants. The most accepted theory today describes the transport of semi-volatile persistent organic pollutants as a temperature and weather dependent repeated deposition and remobilization process between the atmosphere and the ocean and land surface, with a final deposition in the cold northern region. Results also indicate possible new local sources of pesticides in the European Arctic in addition to the long-range transport from more temperate areas.

Persistent organic pollutants in maternal blood plasma and breast milk from Russian arctic populations.

Under the auspices of Arctic Monitoring and Assessment Programme (AMAP), a Russian-Norwegian co-operation project was established to assess the exposure of delivering women to persistent organic pollutants (POPs) in Arctic areas of Russia. In the period 1993-95 blood and breast milk samples were collected from 94 delivering women in Yamal and Tajmyr Autonomous Regions of Siberia. Concentrations of chlorinated pesticides and polychlorinated biphenyls (PCBs) were determined by high resolution gas chromatography with electron capture detection. The POP levels in maternal plasma among the non-indigenous women were higher than the native population, especially in total PCB, HCHs (hexachlorocyclohexanes) and the DDT-group. The dietary questionnaires showed that the non-indigenous populations consumed considerably less local food items like reindeer meat and fresh water fish. There was no correlation between local food consumption and elevated levels of pollutants. Even if the indigenous groups had lower concentrations of the most important pollutants than the non-indigenous population, they were still higher than the levels measured in the Scandinavian countries of the AMAP-study and up to levels of medical concern. The most important sources of organic pollutants for the Russian Arctic populations of Yamal and Tajmyr seems to be imported food from other areas of Russia and local use of pesticides. It must be a high priority concern to further elucidate these trends and initiate prophylactic measures for the exposed population groups.

Effects of docosahexaenoic (22:6n-3), tetracosapentaenoic (24:5n-3) and tetracosahexaenoic (24:6n-3) acids on the desaturation and elongation of n-3 polyunsaturated fatty acids in trout liver microsomes.

The effects of long chain n-3 polyunsaturated fatty acids (PUFA) on the desaturation and elongation systems involved in the conversion of 18:3n-3 to 24:6n-3 were investigated. Microsomes were prepared from the livers of rainbow trout and incubated with 14C-labelled 18:3n-3 and cofactors required for elongation and/or desaturation in the presence of 22:6n-3, 24:5n-3 or 24:6n-3. The formation of 24:6n-3 was significantly inhibited in the presence of 50 microM 22:6n-3, 24:5n-3 or 24:6n-3, whereas the amount of radiolabelled 20:5n-3 formed was inhibited by only 24:5n-3 or 24:6n-3 at the same concentration. When malonyl-CoA was omitted from the incubation system to allow the measurement of desaturation in the absence of elongation, the Delta6 desaturation of 14C-18:3n-3 to 14C-18:4n-3 was inhibited by approximately 25% in the presence of 24:5n-3 or 24:6n-3 but was not affected by 22:6n-3. The Delta5 desaturation of 14C-20:4n-3 was not affected by the presence of any of the long chain PUFA and no significant effect of 18:3n-3, 22:6n-3 or 24:6n-3 on the Delta6 desaturation of 24:5n-3 to 24:6n-3 was observed. To permit the measurement of individual elongation reactions, KCN was included in the incubation medium to inhibit desaturation and 14C-labelled 18:3n-3, 18:4n-3, 20:4n-3, 20:5n-3 and 22:5n-3 were examined as substrates. 18:4n-3 and 22:5n-3 were more extensively used for elongation than 18:3n-3, 20:4n-3 and 20:5n-3. The presence of 22:6n-3, 24:5n-3 or 24:6n-3 in the incubation system had no effect on any of the specific elongations of any of the substrates examined. It is concluded that, in the conversion of 18:3n-3 to 24:6n-3 by trout liver microsomes, the Delta6 desaturation of 18:3n-3 may be subjected to direct feedback inhibition and that 24:5n-3 may be preferred over 18:3n-3 as a substrate for Delta6 desaturation.

Congener specific PCB and polychlorinated camphene (toxaphene) levels in Svalbard ringed seals (Phoca hispida) in relation to sex, age, condition and cytochrome P450 enzyme activity.

Congener specific PCB and toxaphene (polychlorinated camphene, PCC) analyses were performed in seal blubber, collected in Svalbard, Norway. The concentration, body burden and metabolic index (PCB congener concentration in seal relative to their prey) were calculated. Multiple regression analyses were carried out to evaluate the influence of age, sex, blubber (as a percentage of total body weight) and cytochrome P450 activities on PCB and PCC levels. Levels of total PCBs found were five times higher than in ringed seals from the Canadian Arctic, corresponding with the relatively high contaminant levels in the European Arctic. The dominant PCB congeners (> 70% of the total PCBs measured) were 153, 138, 99, 180 and 101. The observed PCB and PCC accumulation patterns were very similar to patterns in seals from other studies, suggesting a large resemblance in contaminant metabolism. A decrease in the relative abundance of the lower chlorinated PCBs, was associated with higher concentrations of PCB 153. Since there was no indication for selective PCB excretion by lactating females, this suggests metabolism of these PCBs in ringed seals due to xenobiotic metabolising enzymes. The metabolic index confirmed the model of persistency of the different PCBs except for congener 128 and 138. These congeners, considered persistent in seals, could to some extent be metabolised in ringed seals. However, co-elution of PCB 138 with PCB 163 and of PCB 128 with TOX 50 possibly has resulted in an underestimation of the metabolic index for these congeners. Multiple regression analyses revealed a significant positive effect of age and a negative effect of the blubber content on the PCB concentrations. Since large fluctuations of body lipids occur between seasons in pinnipeds, PCB measurements should account for the total blubber content to avoid biased results. PCBs with vicinal H-atoms in the o, m or the m, p positions showed in addition a relation with cytochrome P450 enzyme activities. Surprisingly, no effect of sex on the PCB concentrations was observed, probably because female ringed seals, unlike other pinnipeds, continue feeding during lactation. This results in only small amounts of lipid and lipid-associated contaminants being mobilised from the blubber. Consequently, contaminant excretion with the milk will be low. Toxaphene concentrations found were low compared to levels found in the Canadian Arctic. Two congeners, TOX 26 and TOX 50 were predominant (15 and 18%, respectively of total toxaphene). There was no effect of sex, age, total blubber, or cytochrome P450 activities on the toxaphene levels. There was also no correlation between toxaphene and PCB levels, which may indicate differences in exposure and metabolism between these contaminants. Toxaphenes did not bioaccumulate to any substantial extent in ringed seals.

Hydrolysis of fish oils containing polymers of triacylglycerols by pancreatic lipase in vitro.

Fish oils containing different levels of polymers of triacylglycerols formed during autoxidation were incubated with pancreatic lipase to establish whether these polymers are substrates for lipase hydrolysis. With oils containing low amounts (less than 4%) of triacylglycerol polymers as substrates, both triacylglycerols and polymers of triacylglycerols were almost completely hydrolyzed, and fatty acid monomers and monoacylglycerols were the major lipid products. Under the same incubation conditions, some triacylglycerols remained intact when highly oxidized oils containing 20 or 30% triacylglycerol polymers were the substrate. The fatty acid composition of these residual triacylglycerols was almost identical to that of triacylglycerols present at the start of the assay. When fish oil containing 30% triacylglycerol polymers was incubated with the lipase, the component triacylglycerols and polymers of triacylglycerols were hydrolyzed at similar rates, and fatty acid dimers were detected as a product. It is concluded that the high molecular weight polymers of triacylglycerols present in oxidized fish oils can be hydrolyzed by pancreatic lipase in vitro.

The enrichment of n-3 polyunsaturated fatty acids using aminopropyl solid phase extraction columns.

A rapid, simple and reliable method is described for the preparation of concentrates of methyl or ethyl esters of n-3 polyunsaturated fatty acids by solid phase extraction using aminopropyl bonded silica columns. After applying mixtures of fatty acid esters in hexane, saturated and monounsaturated fatty acid esters are preferentially eluted with hexane whereas polyunsaturated fatty acids (PUFA) can subsequently be eluted with dichloromethane. Concentrates containing 80-90% n-3 PUFA can thus be obtained using fish oil fatty acids esters as a starting material.