Development and calibration of epiphytic lichens as saltfall biomonitors--dry-deposition modelling

Blubber collected from beluga whales and ringed seals during subsistence hunts in the southern Baffin Island region of the Canadian Arctic were analysed for polychlorinated naphthalenes and eight planar PCB congeners (mono-ortho PCBs: 105, 114, 118 and 156; non-ortho PCBs: 77, 81, 126, 169). SigmaPCN (3-7 Cl) concentrations in blubber ranged from 35.9-383 pg/g (lipid weight; lw) in beluga and 35.4-71.3 pg/g (lw) in ringed seal. These represent the first measurements of PCNs in marine mammals in the Canadian Arctic, mammals which are an important part of the traditional diet of the indigenous population. SigmaCoplPCB concentrations were much higher, ranging from 15.5-317 ng/g (lw) in beluga whale blubber and 16.5-40.9 ng/g (lw) in ringed seal blubber. PCNs and coplanar PCBs both exhibit dioxin-like toxicity. Although average sigmaPCN concentrations were less than 1% of sigmaCoplPCBs, PCNs contribute up to 11% of TEQ relative to the coplanar PCBs based on TEFs determined by H4IIE enzyme assays.     

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.     

Organohalogenated compounds in pine needles from Beijing city, China

Pine needles collected from 22 sites of six areas in Beijing city, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic extraction for extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The concentrations of EOX (EOX = ECl + EOBr + EOI) were in the order of EOCl > EOBr > EOI. About 1.6-34% of EOCl remained as extractable persistent organochlorine (EPOCl) after treatment with concentrated sulfuric acid, which suggested that major fractions of EOCl in pine needles were an acid-liable or acid-soluble fraction. The fact that pine needle contained higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, HCB and PCBs) to total EOCl and EPOCl were 0.32-0.76% and 2.5-11.4%, respectively, which implied that a major portion of the EOCl and EPOCl measured in pine needles was unknown. The organochlorinated pesticides (OCPs) and PCBs concentrations in six areas were as follows: sigma HCH (sigma HCH = alpha- + beta- + gamma- + delta-HCH), 11.7-20.8 ng/g; sigma DDT (p,p'-DDT + p,p'-DDE + p,p'-DDD), 12.5-113.3 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigma chlordane (cis-chlordane + trans-chlordane + heptachlor), 1.7-9.5 ng/g, sigma PCB, 41.8-270.5 ng/g, on dry weight basis. The samples from chemical industrial area and residential area nearby chemical industries contained the highest concentrations of sigma DDT, HCB, sigma chlordane and sigma PCB, while the contamination levels of most OCPs and PCBs in iron-steel industrial area were the lowest. The ratios of alpha/gamma-HCH (ranged from 0.9-1.5) and p,p'-DDT/DDTs (ranged from 72.1% to 91.0%) revealed the presence of the recent use of lindane and DDTs or impure dicofol in Beijing.     

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.     

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.     

PCBs, DDTs and methyl sulphone metabolites in various tissues of harbour porpoises from Swedish waters

Aryl methyl sulphones of polychlorinated biphenyls (PCBs) and 3-p,p'-DDE (MeSO(2)-PCBs and 3-MeSO(2)-p,p'-DDE), PCBs and Sigma DDTs were analysed in five different tissues (blubber, nuchal fat, liver, muscle, brain) of adult male harbour porpoises from the west coast of Sweden. Two different methods for MeSO(2)-PCBs and 3-MeSO(2)-p,p'-DDE determination were used, gas chromatography-mass spectrometry and gas chromatography-atomic emission detection. Highest concentrations of Sigma MeSO(2)-PCBs were found in liver (0.15-0.49 microg/g lipid wt.), which corresponded to 2.0-2.8% of the Sigma PCBs concentrations. Blubber and nuchal fat showed Sigma MeSO(2)-PCB concentrations that were three to five times lower than those in liver. Concentrations of 3-MeSO(2)-p,p'-DDE in liver, muscle and brain corresponded to 0.26-4.6% of the p,p'-DDE concentrations, while in blubber and nuchal fat, 3-MeSO(2)-p,p'-DDE constituted 0.033-0.21% of p,p'-DDE. The different tissues analysed showed similar levels (lipid wt.) of Sigma PCBs and Sigma DDTs, except for brain that had almost 10 times lower levels compared to the other tissues. Using the Sigma PCBs/Sigma MeSO(2)-PCBs ratio to estimate MeSO(2)-PCB formation and secondary metabolism capacity, the harbour porpoise showed a relatively low capacity of MeSO(2)-PCB formation compared to other small toothed whales and seals. Blubber sampled from five different anatomical locations showed that concentrations of contaminants may be unevenly distributed in blubber in certain animals. This should be taken into account when choosing sampling sites on the porpoise.     

Tris (4-chlorophenyl) methane and tris (4-chlorophenyl) methanol in marine mammals from the Estuary and Gulf of St. Lawrence

Levels of tris (4-chlorophenyl) methanol (TCPM) and its presumed precursor tris (4-chlorophenyl) methane (TCPMe) are reported in marine mammals from the Estuary and Gulf of St. Lawrence, Canada. These compounds were measured in blubber samples of seals and whales using ion trap mass spectrometry (MS/MS) detection. Detectable concentrations of both TCPM and TCPMe were observed in all of the samples analysed. Concentrations of these compounds varied with species ranging from 1.7 to 153 and from 1.3 to 50.6 ng/g lipid wt. for TCPM and TCPMe, respectively. TCPM was from 1.3 to 10 times more concentrated than TCPMe. The highest levels of both TCPM and TCPMe were observed in adult male beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, while adult female beluga whales from the same area showed levels similar to those in the seals examined. Among the four seal species investigated, TCPM and TCPMe levels were the highest in grey (Halichoerus grypus) and hooded (Cystophora cristata) seals, and lowest in harp seals (Phoca groenlandica). Intermediate levels were found in harbour seals (Phoca vitulina); however, their concentrations might be underestimated considering the younger mean age of these animals. Ratios of both 4,4'-DDE/sigma DDT and TCPM/sigma TCP were very similar between animals from the same species. Strong correlations between sigma TCP and sigma DDT were also observed for each species of mammals, most likely indicating that both sigma TCP and sigma DDT are bioaccumulated in marine mammals. The relationships between sigma DDT and sigma TCP also demonstrate that sigma TCP are less bioaccumulated than sigma DDT by the marine mammal species examined.     

Levels of selected individual polychlorinated biphenyls in different tissues of harbour seals (phoca vitulina) from the Southern coast of Norway

Concentrations of individual polychlorinated biphenyls (PCBs) were determined in blubber, liver, kidney and brain tissues of 10 male harbour seals (Phoca vitulina) of different ages. The animals were found dead or dying on the southern coast of Norway in 1988 during the morbilli virus epizootic. Twenty-three PCB congeners were investigated in all tissues by capillary gas chromatography with electron capture detection and comparison with standards of the respective congeners (IUPAC numbers 28, 52, 74, 99, 101, 105, 110, 114, 118, 128, 138, 141, 149, 153, 156, 157, 170, 180, 183, 187, 194, 206 and 209). In addition, three toxic coplanar congeners (IUPAC numbers 77, 126 and 169) were investigated in the blubber samples. Total PCB (sum of the determined congeners) in kidney (12-60 nmol g(-1)), liver (12-90 nmol g(-1)) and blubber (10-79 nmol g(-1)) were similar on extractable lipid basis, while total PCB in brain lipid was about 1/10 (1.6-12 nmol g(-1)). The absolute concentrations of the individual congeners in brain lipid correlated poorly with the respective concentrations in each of the other tissues, while the individual congener concentrations in the lipid fractions of kidney, liver and blubber tended to correlate with each other. The relative concentrations of the sum of the most persistent congeners (PCB-99, -128, -138, -153, -170, -180, -187 and -194) correlated in all tissues, and an increase of the relative concentrations of these congeners, most distinct in blubber, with higher carcass weight, was shown. Also, total PCB in blubber correlated with carcass weight. When comparing the relative concentration patterns of individual congeners (per cent of total) in the four tissues, six congeners differed significantly between tissues, and the relative brain concentrations showed most deviation from the other tissues. The concentration of the coplanar PCBs was 1 : 1000-1 : 1000 of the total PCB concentration. The results demonstrate a lower accumulation together with a different concentration pattern in the brain as compared to other tissues.     

Chemical contaminants in juvenile gray whales (Eschrichtius robustus) from a subsistence harvest in Arctic feeding grounds

Gray whales are coastal migratory baleen whales that are benthic feeders. Most of their feeding takes place in the northern Pacific Ocean with opportunistic feeding taking place during their migrations and residence on the breeding grounds. The concentrations of organochlorines and trace elements were determined in tissues and stomach contents of juvenile gray whales that were taken on their Arctic feeding grounds in the western Bering Sea during a Russian subsistence harvest. These concentrations were compared to previously published data for contaminants in gray whales that stranded along the west coast of the US during their northbound migration. Feeding in coastal waters during their migrations may present a risk of exposure to toxic chemicals in some regions. The mean concentration (standard error of the mean, SEM) of sigmaPCBs [1400 (130) ng/g, lipid weight] in the blubber of juvenile subsistence whales was significantly lower than the mean level [27,000 (11,000) ng/g, lipid weight] reported previously in juvenile gray whales that stranded in waters off the west coast of the US. Aluminum in stomach contents of the subsistence whales was high compared to other marine mammal species, which is consistent with the ingestion of sediment during feeding. Furthermore, the concentrations of potentially toxic chemicals in tissues were relatively low when compared to the concentrations in tissues of other marine mammals feeding at higher trophic levels. These chemical contaminant data for the subsistence gray whales substantially increase the information available for presumably healthy animals.     

A comparative evaluation of accelerated solvent extraction and Polytron extraction for quantification of lipids and extractable organochlorine in fish

Optimal conditions for extraction methods using an accelerated solvent extractor (ASE) and a Polytron homogenizer were established for quantification of (crude) lipids and extractable organochlorine (EOCl) in fish. The two methods, an ASE consecutive extraction at 55 and 100 degrees C for ground, freeze-dried filets, and a Polytron extraction at room temperature with four repetitions for ground, wet filets and with two repetitions for wet fish livers were evaluated in terms of reproducibility and comparability. With respect to lipid measurement, the two methods have comparable reproducibility and the experimental errors are relatively small compared to natural variations of fish to fish within a sampling site. For EOCl measurement, the relative standard deviation tends to increase with decreasing levels of EOCl in specimens. An important factor for the relative standard deviation of measurements of analytes present at trace levels in fish matrices is sampling error in taking aliquots. Statistical analysis using a paired comparison design showed that measurement values (crude lipids or EOCl) obtained from these two extraction methods are, in general, not equivalent. There is a good correlation between the two methods for lipid measurement; whereas for EOCl measurements, high degrees of correlation exist within the exposed fish group, but not in the reference group.     

Tissue distribution of polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) in harbour porpoises (Phocoena phocoena) from Swedish waters

Polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) were analysed in blubber, nuchal fat, liver, muscle, kidney and brain of three male harbour porpoises (Phocoena phocoena) from the west coast of Sweden. To estimate spatial variation, PCNs and non-ortho CBs were analysed in six blubber samples collected at different anatomical sites of each animal. Highest wet weight concentrations of ΣPCNs were detected in the lipid rich tissues (blubber and nuchal fat) and liver (520–730 and 520 pg/g, respectively) and lowest in brain (22 pg/g). TetraCNs were most abundant in muscle, kidney and brain, while the hexaCNs were most abundant in the lipid rich tissues and liver. The highest lipid weight concentration recorded (11 ng/g) was for the hexaCN congeners no. 66/67 in liver. These coeluting hexaCN congeners accounted for 80–100% of total hexaCNs in all tissues examined.

Concentrations of Σnon-ortho CBs were highest in lipid rich tissues (220–280 pg/g wet weight). Non-ortho CB no. 77 and 169 constituted between 62–86% and 4.9–9.3%, respectively, of total Σnon-ortho CBs. No major variation of Σnon-ortho CB concentrations was found between the six different blubber sites but higher ΣPCN concentrations (wet weight) were found dorsally at the peduncle. Toxic equivalent concentrations (TEQs) showed that non-ortho CB no. 126 was the main contributor to total TEQs in all tissues, except liver in which hexaCN congener nos. 66/67 contributed to about 50% of total TEQs.     

Levels and patterns of persistent organochlorines in minke whale (Balaenoptera acutorostrata) stocks from the North Atlantic and European Arctic

Regional variation in PCBs and organochlorine (OC) pesticide concentrations was examined using the blubber of 155 minke whales (Balaenoptera acutorostrata) sampled in seven regions in the North Atlantic and European Arctic, including western and southeastern Greenland, the Norwegian Sea, the North Sea and the Barents Sea. The levels and relative proportions of OCs were also used to examine the boundaries for North Atlantic minke whale stocks previously defined by the International Whaling Commission (IWC). Concentrations of major OC groups (sigmaPCB, 89.1-22 800 ng/g lipid; sigmaDDT, 65.3-6280 ng/g lipid; sigmaCHL, 33.3-2110 ng/g lipid) generally increased from west to east, while HCH concentrations (sigmaHCH, < 1-497 ng/g lipid) showed the opposite trend. Statistical comparison between six regions using sex-adjusted least squared mean concentrations showed that minke whales from the Barents Sea had significantly higher concentrations of EPCBs than those from the Vestfjorden/Lofoten, the North Sea, and west Svalbard, as well as significantly higher sigmaDDT concentrations compared to west Greenland animals. The differences in concentrations suggest that west and southeast Greenland minkes may represent one group of whales, which are distinct from both the Jan Mayen minkes and those from other IWC defined stocks in northern European waters. Principal components analysis using proportions of 71 PCB congeners and 20 OC pesticides (of total OCs) did not reveal any major differences among groups although minkes from the North Sea were distinguished from those from Greenland waters by higher loadings of more highly chlorinated PCBs and recalcitrant OC pesticides. The general similarity in mean levels of sigmaPCBs, sigmaDDT and sigmaCHL, as well as mean principal components analysis scores, among minkes sampled at Jan Mayen, Svalbard, Vestfjorden/Lofoten, the North Sea and the Barents Sea suggests that the whales are quite mobile and may feed in multiple areas within the northeastern Atlantic.     

Mercury induced time-dependent alterations in lipid profiles and lipid peroxidation in different body organs of cat-fish Heteropneustes fossilis

The effects of mercuric chloride (HgCl2) on lipid profiles and lipid peroxidation in different body organs of fresh water cat-fish Heteropneustes fossilis were studied. The daily exposure of HgCl2 0.2 mg/L for 10, 20 and 30 days depleted the total lipids in brain. But the content of phospholipids enhanced significantly at 30 days. Significant diminution in C/P ratio was discernible with 30 days of exposure following mercury toxicosis. Liver exhibited elevated levels of total lipids, phospholipids, cholesterol and C/P ratio. Interestingly kidney showed marked decrease in the concentration of total lipids, cholesterol and C/P ratio at higher exposure. However, the phospholipid values increased during the longer exposure. The content of total lipids and phospholipids was high in muscle but the level of cholesterol and C/P ratio were depleted. Significant increment in lipid peroxidation was discernible in brain, liver and muscle. In kidney the rate of lipid peroxidation was significantly reduced. The results suggest that exposure of HgCl2 enhances the peroxidation of endogenous lipids in brain, liver and muscle. Interestingly the lipid contents are affected differently in different body organs.     

Tissue distribution of polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) in harbour porpoises (Phocoena phocoena) from Swedish waters

Polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) were analysed in blubber, nuchal fat, liver, muscle, kidney and brain of three male harbour porpoises (Phocoena phocoena) from the west coast of Sweden. To estimate spatial variation, PCNs and non-ortho CBs were analysed in six blubber samples collected at different anatomical sites of each animal. Highest wet weight concentrations of ΣPCNs were detected in the lipid rich tissues (blubber and nuchal fat) and liver (520–730 and 520 pg/g, respectively) and lowest in brain (22 pg/g). TetraCNs were most abundant in muscle, kidney and brain, while the hexaCNs were most abundant in the lipid rich tissues and liver. The highest lipid weight concentration recorded (11 ng/g) was for the hexaCN congeners no. 66/67 in liver. These coeluting hexaCN congeners accounted for 80–100% of total hexaCNs in all tissues examined.Concentrations of Σnon-ortho CBs were highest in lipid rich tissues (220–280 pg/g wet weight). Non-ortho CB no. 77 and 169 constituted between 62–86% and 4.9–9.3%, respectively, of total Σnon-ortho CBs. No major variation of Σnon-ortho CB concentrations was found between the six different blubber sites but higher ΣPCN concentrations (wet weight) were found dorsally at the peduncle. Toxic equivalent concentrations (TEQs) showed that non-ortho CB no. 126 was the main contributor to total TEQs in all tissues, except liver in which hexaCN congener nos. 66/67 contributed to about 50% of total TEQs.     

Contamination by mercury and cadmium in the cetacean products from Japanese market

Cetaceans hunted coastally in Japan include several species of odontocete (dolphins, porpoises and beaked whales), and fresh and frozen red meat and blubber, as well as boiled internal organs, such as liver, lung, kidney and small intestine, are still sold for human consumption. Furthermore, red meat and blubber products originating from mysticete minke whales caught in the Antarctic and Northern Pacific are also sold for human consumption. We surveyed mercury and cadmium contamination levels in boiled liver, lung, kidney and red meat products being marketed in Japanese retail outlets. We also analyzed the DNA of these products to obtain information concerning gender and species. Total mercury (T-Hg) and methyl mercury (M-Hg) contamination levels in all the cetacean products were markedly higher in odontocete species than in mysticete species, and slightly higher in females than in males. T-Hg contamination in the organs was seen in the following order: boiled liver > boiled KIDNEY=boiled lung > red meat. In particular, T-Hg concentrations in the boiled liver were high enough to cause acute intoxication even from a single ingestion: the mean ±SD (range) of T-Hg was 388 ± 543 (0.12–1980) μg/wet g. In contrast, although M-Hg contamination in the liver was not markedly higher than that in other organs, M-Hg contamination was in the following order: boiled liver > odontocete red meat > boiled kidney > boiled lung. The contamination levels of T-Hg and M-Hg in odontocete red meat, the most popular whale product, were 8.94 ± 13.3 and 5.44 ± 5.72 μg/wet g, respectively. These averages exceeded the provisional permitted levels of T-Hg (0.4 μg/wet g) and M-Hg (0.3 μg/wet g) in marine foods set by the Japanese Ministry of Health, Labor and Welfare by 22 and 18 times, respectively, suggesting the possibility of chronic intoxication by T-Hg and M-Hg with frequent consumption of odontocete red meat. Cadmium contamination levels in boiled liver, kidney and lung were 8.59 ± 12.0, 10.4 ± 8.6 and 1.66 ± 1.27 (μg/wet g), respectively.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--II. Temporal trends, 1982-1994

Blubber samples from 16 dead beluga whales (Delphinapterus leucas) collected during 1993-1994 in the St Lawrence River estuary were analysed for PCB congeners and other persistent organochlorines (DDT-group, chlorinated bornanes (toxaphene, CHB), chlordane SigmaCHL), hexachloro-cyclohexanes (SigmaHCH), chlorobenzenes (SigmaCBz), tris(p-chlorophenyl methane (TPMe) and mirex). Concentrations and relative proportions of major individual organochlorine components were within the same range as previous results for this population. Temporal trends were studied by combining the results with data from the analysis of 44 samples (1986-1990) and (for DDT and Aroclor PCBs only) with 20 samples (1982-1985) reported by Martineau et al., 1987. Results were lipid normalized and then age-adjusted by an ANCOVA model. Significant relationships between age and concentrations of most organochlorine groups were found for females but not for males. Significant declines were observed in SigmaDDT, and Aroclor PCBs (1.5- and 1.9-fold, respectively) in males between the 1982-1985 and 1993-1994 collection periods. Significant declines were also observed for SigmaHCH and SigmaCBz in males between 1986-1988 and 1993-1994. Mean concentrations of CHBs were significantly higher in 1993-1994 than in earlier years while dieldrin, SigmaCHL, mirex, and TPMe showed no trend. Declines in concentrations of major organochlorine groups were not observed in females possibly because of higher year to year, and within year, variation. The temporal trend in DDT and PCB concentrations in male beluga blubber paralleled trends in seals, eels, and seabirds in the St Lawrence estuary observed during the 1980s.     

Temporal and biogeographic comparisons of PCBs and persistent organochlorine pollutants in the blubber of fin whales from eastern Canada in 1971-1991

Concentrations of PCB congeners and organochlorine (OC) pesticides were studied in archived fin whale (Balaenoptera physalus) blubber samples collected in 1971-1972 from Newfoundland (Nfld) and Nova Scotia (NS) with the objective of obtaining a historical perspective on contaminant levels and proportions at a time when many persistent OCs were still in use. Concentrations of sigmaPCBs and sigmaDDTs in the blubber of 17 fin whales from historical whaling stations in 1971-1972 were generally in agreement with previously reported values for fin whales from Atlantic Canada. Although some differences in sex and body length (age) distribution of samples occurred, significant differences were detected in the concentrations and patterns of PCBs, DDTs and chlordanes in whales from Nfld and NS, supporting ecological evidence that whales from these regions represent relatively separate stocks. Temporal and geographical variations were examined by comparing data to those reported for fin whales from the St Lawrence Estuary (StL) in 1991 by Gauthier et al. (1997a). Significantly higher levels of sigmaDDT, sigmaCHL and HCB were found in the NS (1971-1972) stock compared with the StL (1991) animals, and in HCB between the Nfld stock (1971-1972) and the StL (1991) animals, as well as higher p,p'-DDE/sigmaDDT and lower p,p'-DDT/sigmaDDT ratios in the 1991 whales suggesting that temporal trends in these whales between the 1970s and 1990s were consistent with those in other marine mammals in Atlantic Canada. Evidence also suggests that geographical variations in patterns may occur for individuals from two relatively distinct stocks of fin whales in Atlantic Canada (NS, Nfld) and perhaps for one population (StL) related to, but recognisably different from the NS stock.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

Trace elements in two odontocete species (Kogia breviceps and Globicephala macrorhynchus) stranded in New Caledonia (South Pacific)

Liver, muscle and blubber tissues of two short-finned pilot whales (Globicephala macrorhynchus) and two pygmy sperm whales(Kogia breviceps) stranded on the coast of New Caledonia have been analysed for 12 trace elements (Al, Cd, Co, Cr, Cu. Fe, organic and total Hg, Mn, Ni, Se, V, and Zn). Liver was shown to be the most important accumulating organ for Cd, Cu, Fe, Hg, Se, and Zn in both species, G. macrorhynchus having the highest Cd, Hg, Se and Zn levels. In this species, concentrations of total Hg are particularly elevated, reaching up to 1452 microg g(-1) dry wt. Only a very low percentage of the total Hg was organic. In both species,the levels of Hg are directly related to Se in liver. Thus, a molar ratio of Hg:Se close to 1.0 was found for all specimens, except for the youngest K. breviceps. Our results suggest that G. macrorhynchus have a physiology promoting the accumulation of high levels of naturally occurring toxic elements. Furthermore, concentrations of Ni, Cr and Co are close to or below the detection limit in the liver and muscles of all specimens. This suggests that mining activity in New Caledonia, which typically elevates the levels of these contaminants in the marine environment, does not seem to be a significant source of contamination for these pelagic marine mammals.     

Biochemical study on the protective role of folic acid in rabbits treated with chromium (VI)

Deleterious effects of chromium (VI) compounds are diversified affecting almost all the organ systems in a wide variety of animals. Therefore, the present study was carried out to determine the effectiveness of folic acid (FA) in alleviating the toxicity of chromium (VI) on certain biochemical parameters, lipid peroxidation, and enzyme activities of male New Zealand white rabbits. Six rabbits per group were assigned to one of four treatment groups: 0 mg FA and 0 mg Cr(VI)/kg BW (control); 8.3 microg FA/kg BW; 5 mg Cr(VI)/kg BW; 5 mg Cr(VI) plus 8.3 microg FA/kg BW, respectively. Rabbits were orally administered their respective doses every day for 10 weeks. Results obtained showed that Cr(VI) significantly (P < 0.05) increased the levels of free radicals and the activity of glutathione S-transferase (GST), and decreased the content of sulfhydryl groups (SH groups) in liver, testes, brain, kidney, and lung. The activities of aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (AlP), acid phosphatase (AcP), and lactate dehydrogenase (LDH) were significantly decreased in liver and testes due to Cr(VI) administration. Also, AlP and AcP activities were significantly decreased in kidney and lung. The activity of acetylcholinesterase (AChE) was significantly decreased in brain and plasma. Contrariwise, the activities of AST and ALT were significantly increased in plasma, while AlP and AcP decreased. Chromium (VI) treatment caused a significant decrease in plasma total protein (TP) and globulin, and increased total lipids (TL), cholesterol, glucose, urea, creatinine, and bilirubin concentrations. Folic acid alone significantly decreased the levels of free radicals in liver, brain, and kidney, and increased the content of SH-group. The activities of AST, ALT, and LDH in liver; AST, ALT, AlP, AcP, and LDH in testes; AcP in kidney; AlP and AcP in lung, and LDH in brain were significantly increased. Plasma TP and albumin were increased, while urea and creatinine were decreased. The presence of FA with Cr(VI) restored the changes in enzyme activities and biochemical parameters. In conclusion, folic acid could be effective in the protection of chromium-induced toxicity.