Accumulation of heavy metals in Caspian seals (Phoca caspica).

Concentrations of heavy metals (Fe, Mn, Zn, Cu, Pb, Ni, Cd, Co, and Hg) were determined in the muscle, liver, and kidney of 42 Caspian seals and fishes collected from the Caspian Sea in 1993. Higher Mn and lower Fe and Cu concentrations were found in the liver in comparison with other marine pinnipeds. Lower Cu concentrations in the liver appear to be a common feature in small seals belonging to subgenus Pusa, which include ringed, Baikal, and Caspian seals. However, low Fe and high Mn in livers were specific to Caspian seal. Concentrations of toxic metals such as Hg and Cd were relatively low. Pinniped species can be divided into two groups, based on accumulations of Cd or Hg in the liver. Interestingly, it was found that Cd-accumulating groups feed on invertebrates, whereas the preferred diet of Hg accumulators is fish. Caspian seals seemed to belong to the Hg-accumulating group.Cd and Hg concentrations in the liver and kidney of young animals increased with age. Mercury concentrations in adult animals increased with age continuously, whereas Cd concentrations in adult animals decreased. This trend might be due to preferential feeding habits and shift in ratio of Hg and Cd in the diet ( i.e., invertebrates to fish).

Accumulation of silver in the liver of three species of pinnipeds.

Silver in the three species of pinnipeds [northern fur seal (Callorhinus ursinus), Steller sea lion (Eumetopias jubatus), and harbor seal (Phoca vitulina)] caught in the North Pacific Ocean were analyzed using inductively coupled plasma-mass spectrometry, in order to understand accumulation and distribution of silver in pinnipeds. In northern fur seals, relatively high concentrations of silver were observed in the liver and body hair. Some 70% of the silver burden was concentrated in the liver. Hepatic silver concentrations were significantly correlated to age in northern fur seals (r = 0.766, P < 0.001, n = 49) and Steller sea lions (r = 0.496, P < 0.01, n = 28). Levels of silver concentrations per wet weight (microgram g-1) in the three pinnipeds ranged from 0.04 to 0.55 for northern fur seals, from 0.1 to 1.04 for Steller sea lions and from 0.03 to 0.83 for harbor seals. Silver concentrations in liver for all pinnipeds were significantly correlated with mercury, and selenium (P < 0.001). Molar ratios between silver to selenium approximated 1:180 in northern fur seals, 1:120 in Steller sea lions, and 1:60 in harbor seals. The silver-mercury molar ratios were approximately 1:170 in northern fur seals, and 1:80 both in the other species. Increase in silver accumulation in the liver was caused by the retention in nuclei and mitochondria fraction together with mercury and selenium in the cells of northern fur seals.

Growth-related changes in heavy metal accumulation in green turtle (Chelonia mydas) from Yaeyama Islands, Okinawa, Japan.

Concentrations of nine heavy metals (Fe, Mn, Zn, Cu, Pb, Ni, Cd, Co, and Hg) were determined in liver, kidney, and muscle of 50 green turtles (Chelonia mydas) collected from Yaeyama Islands, Okinawa, Japan, to elucidate growth-related changes in heavy metal accumulation during different growth stage. Considerably high Cu concentrations were found in the liver of smaller turtles. Mean hepatic concentration of Cu was 50.2 microg/g wet weight which varied widely (4.27-113 microg/g wet weight). Cadmium concentrations decreased with increasing the carapace length. The juvenile green turtles in the pelagic ocean are likely feed on zooplankton, while adult coastal inhabiting green turtles mainly feed on sea grasses and seaweeds. Concentrations of Cd in sea plants are lower than those in zooplankton. The specific accumulation of Cd found in the green turtle seems to be attributable to their feeding habit, which is a shift from carnivore to herbivore at different growth stages.

Mercury and cadmium in common cormorants (Phalacrocorax carbo).

Mercury (Hg) and cadmium (Cd) in common cormorants (Phalacrocorax carbo) collected in Lake Biwa, Japan and Tokyo, Japan, were investigated to elucidate the biological behaviors of these elements, and to assess exposure to these pollutants of wild, fish-eating birds. Hg and Cd concentrations were highest in the liver and kidneys, respectively. The lowest levels of both elements were observed in chicks. Hg concentrations in all tissues except brain increased significantly with growth from chicks to juveniles (p<0.05, U-test). Cd concentrations in the kidneys and liver also increased significantly during growth from juvenile to adult (p<0.005, U-test). When comparing hepatic Hg and Cd in adult birds between 10 samples from Lake Biwa and nine samples from Tokyo, the Cd concentrations in the Lake Biwa samples (1.4+/-0.37 microg/g dry wt) (mean+/-SD) were significantly higher than those from Tokyo (0.32+/-0.16 microg/g dry wt) (p<0.005, U-test), while no statistically significant difference was found in the Hg concentrations. Possible causes of these differences were discussed in relation to their prey.

Contamination levels and specific accumulation of persistent organochlorines in Caspian seal (Phoca caspica) from the Caspian sea, Russia.

Persistent organochlorines, such as polychlorinated biphenyls (PCBs) including coplanar congeners, DDTs, HCHs, chlordanes (CHLs), and HCB, were determined in the blubber of Caspian seals (Phoca caspica) and their fish diet (Rutilus sp.) collected in 1993 from the northern Caspian Sea, Russia. Notable concentrations of DDTs and HCHs were found at mean values of 19 and 1.3 microg/g on wet-weight basis in adult male seals, respectively. PCB pollution in Caspian seals was not so considerable compared with those of seals that suffered mass mortality. Less gender difference of organochlorine residue levels in adult animals implies less excretion of organochlorines from the body of adult females through lactation and gestation, probably due to the higher rate of pregnancy failure. Immature seals had a wide range of organochlorine concentrations, which decreased as body length increased, suggesting dilution. Caspian seals can be considered to have higher degradation capacity for coplanar PCBs. Mean TEQs (2,3,7,8-TCDD toxic equivalents) for non-, mono- and di-ortho coplanar PCBs was 51 pg/g on wet-weight basis, which was lower than those in seals that have suffered mass mortality, but comparable to those found in Arctic seals.

Vanadium accumulation in pinnipeds.

Vanadium in four species of pinnipeds (northern fur seals [Callorhinus ursinus], Steller sea lions [Eumetopias jubatus], harbor seals [Phoca vitulina], and ribbon seals [Phoca fasciata]) caught in the Northern Pacific was analyzed using ICP-MS to understand its accumulation and distribution. In northern fur seals, relatively high concentrations of vanadium were observed in the liver, hair, and bone. Ninety percent of the vanadium burden in the body was concentrated in these three tissues, which comprise <20% of total body weight. Hepatic vanadium concentrations in the four pinniped species were significantly correlated to age, although the levels varied with species. An increase in vanadium accumulation in the liver of northern fur seals was caused by an increase of retention in nuclei and mitochondria fraction in the cells. Vanadium concentrations in liver were significantly correlated with mercury, silver, and selenium concentrations in northern fur seals, Steller sea lions, and harbor seals.

Distribution of 14 elements in tissues and organs of oceanic seabirds.

The concentrations of 14 trace elements (Li, V, Mn, Co, Cu, Zn, Se, Rb, Sr, Ag, Cd, Cs, Pb, and Hg) were determined in tissues and organs of three species and in the liver of 11 species of seabirds. Comparatively high concentrations of Li, Co, Sr, and V were found in the femur. Cd, Se, Cu, and Mn concentrations were relatively higher in the kidney than in other tissues and organs. Rb, Cs, and Pb concentrations were rather uniform among tissues. Concentrations of essential elements such as Mn, Cu, and Co were comparable among seabird species, except high Cu concentrations in northern giant petrel. Among nonessential elements, concentrations of Cd and Hg were variable according to seabird species. Pb levels were low in all the species. High Se levels (100 microg/g dry weight) were found in the liver of black-footed albatross and grey petrel. There were significant positive correlations between Se and Cd concentrations in three species and between Se and Hg in black-footed albatross, suggesting that Se has an antagonistic action on the toxic effects of Cd and Hg. Concentrations of Li, V, Ag, and Cs were usually low (less than 1 microg/g dry weight).

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: interspecies comparison of the residue levels and compositions.

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2', 3, 4, 4', 5, 5'-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2', 4, 4', 5, 5'-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.

Age-dependent accumulation of heavy metals in baikal seal (Phoca sibirica) from the Lake Baikal.

Concentrations of Fe, Mn, Zn, Cu, Cd, and Hg were determined in the liver, kidney, and muscle of 60 Baikal seals collected from Lake Baikal in 1992 to investigate age-dependent accumulation. Among essential elements, Fe concentrations in the muscle, liver, and kidney increased with age, suggesting development of diving ability. The concentrations of Mn, Zn, and Cu decreased with age, especially at immature stages. Toxic elements such as Hg and Cd decreased in adult males and thus the male-female difference was clearly observed in their concentrations, which differed from patterns usually found in marine mammals. Such accumulation patterns were due to difference in the feeding rates between males and females under low exposure to Hg and Cd. In addition, a greater excretion of Hg than that of Cd through molting and parturition was estimated.

Organochlorine pesticides and polychlorinated biphenyls in foodstuffs from Asian and oceanic countries.

Public concern about the adverse environmental and human health impacts of organochlorine contaminants led to strict regulations on their use in developed nations two decades ago. Nevertheless, DDT and several other organochlorine insecticides are still being used for agriculture and public health programs in developing countries in Asia and the South Pacific. As a consequence, humans in this region are exposed to greater dietary levels of organochlorines. In this review, published information on organochlorine concentrations in foodstuffs from South and Southeast Asia and Oceanic countries has been compiled. Foodstuffs that contribute to human exposures and dietary intakes of organochlorines were examined, and the data compared with those reported from more developed nations. Among various developing countries in Asia, considerable information on organochlorines in foodstuffs has been available from India since the late 1960s. DDT and HCH were the major insecticides in Indian foodstuffs. Concentrations of these insecticides have declined more than two orders of magnitude in farm products, such as food grains and vegetables, in two decades. Milk and milk products are the major sources of dietary exposure to DDT and HCH in India. The residues of these insecticides in dairy products were close to or above the MRLs of the FAO/WHO. Dietary intake of DDT and HCH by Indians was > 100 fold that in more developed nations. Sporadic incidences of greater concentrations (> 1 microgram/g) of aldrin, dieldrin, and heptachlor have been measured in Indian vegetables. Untreated surface waters could be a potential source of DDT and HCH exposure. In most Southeast Asian countries DDT was the common contaminant in animal origin foodstuffs. The higher percentage of p,p'-DDT in meat and fish from Southeast Asian countries, except Japan and Korea, indicated the recent use of DDt in vector control operations. Dietary intakes of DDt and HCH in Southeast Asia were an order of magnitude less than those of Indians but 5- to 10 fold greater than in more developed nations. In addition to DDT, aldrin and dieldrin were prominent in meat collected from Thailand and Malaysia. Aquatic food products from more industrialized countries, such as Japan, South Korea, Hong Kong, and Taiwan, contained significant levels of PCBs. In South Pacific countries, particularly in Australia and New Zealand, chlordanes and PCBs were the most prevalent organochlorines in foodstuffs. Food contamination by DDT, HCH, aldrin, and dieldrin was less than in developing countries in Asia but greater than in the U.S. and Japan. Intake of PCBs in Australia was greater than in the U.S. Meat and fish were the major sources of organochlorine exposure by Australians. Human dietary intake of organochlorines has been declining more slowly in developing countries in Asia. Current intakes were at least 5- to 100 fold greater than those in more developed nations, suggesting a greater risk from organochlorine exposure. Factors such as malnutrition, common among rural poor in developing nations, can increase these risks. Of greatest concern is the magnitude of exposure to organochlorines to which infants and children are subjected through human and dairy milk. The estimated intake of DDT by infants was at least 100 fold greater than the ADI of the FAO/WHO. In addition to DDT, excessive exposures to HCH and dieldrin may cause potential health effects in infants because they are more vulnerable to toxic effects. The design and implementation of appropriate epidemiological studies and their integration with monitoring of human, food, and environmental samples would be a major step in assessing the risks of organochlorine residues in foods and controlling or eliminating them. With the continued globalization of trade in food products, and the concomitant risk that food contaminated through point-source pollution may be widely distributed, identification of sources and their control should be matters of

Persistent organochlorines in minke whale (Balaenoptera acutorostrata) and their prey species from the Antarctic and the North Pacific.

Persistent organochlorines such as polychlorinated biphenyls (PCBs), DDTs, chlordane compounds (CHLs), hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were determined in the blubber of minke whale and its diet collected from the Antarctic and the North Pacific Oceans. Residue levels of these compounds (except HCB) in minke whale from the Antarctic were apparently lower than those from the North Pacific. This is due to the lower levels of these pollutants in the southern hemisphere than in the northern hemisphere and the specific feeding habit of the minke whale from the Antarctic which feeds on lower trophic organisms, primarily euphausiids. The north-south difference for HCB residue levels was small, reflecting its dispersible nature through long-range atmospheric transport. Compositions of DDT and CHL compounds in minke whale from the Antarctic were similar to those from the North Pacific. However, the composition of HCH isomers was different between the Antarctic and the North Pacific as was observed in their diet, suggesting a larger or on-going usage of lindane in the southern hemisphere countries. In minke whale from the Antarctic, the elevated level of PCBs residues was noted during a period of 1984 to 1993, implying a continuous discharge of PCBs in the southern hemisphere. A similar discharge was also suggested in the North Pacific, while a decreasing contamination by DDTs was apparent.

Bioaccumulation profiles of polychlorinated biphenyls including coplanar congeners and possible toxicological implications in Baikal seal (Phoca sibirica).

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169), mono-ortho (105, 118, 156) and di-ortho (137, 138, 153, 180) coplanar congeners were determined in the blubber of 40 Baikal seals (Phoca sibirica) and as their fish diet collected from Lake Baikal, Siberia. Residue levels of total PCBs in Baikal seals were noticeably high and comparable to those reported for seals from the North Sea, suggesting the recent usage of this compound in the watershed of Lake Baikal. Non-, mono-, and di-ortho coplanar congeners were also detected in Baikal seals and fish. An approach to estimate bioaccumulation profiles of PCB congeners revealed that the non-ortho PCBs, IUPAC 77, 126 and 169 seemed to be less persistent than other congeners. Furthermore, selective biotransformation of PCB congeners having either meta-para vicinal H atoms or both adjacent chlorinated meta-para and ortho-meta positions has been suggested. Comparison of 2,3,7,8-TCDD toxic equivalents (TEQ) of non-, mono- and di-ortho coplanar congeners in Baikal seals with those for other marine mammals suggested higher enrichment of mono-ortho congeners, particularly IUPAC 105 and 118, which contributed significantly to the total TEQs in Baikal seals. Results imply that the TCDD-like toxicity is relatively serious in Baikal seals, because of the enrichment of these toxic PCB congeners in tissues.

Accumulation pattern of butyltin compounds in dolphin, tuna, and shark collected from Italian coastal waters.

Tributyltin (TBT) and its breakdown products, mono-(MBT) and dibutyltin (DBT) were determined in bottlenose dolphin (Tursiops truncatus), bluefin tuna (Thunnus thynnus thynnus) and blue shark (Prionace glauca) collected from the Italian coast of the Mediterranean Sea in 1992-1993. Concentrations of total butyltin (BTs) in the liver of dolphin (1,200-2,200 ng/g wet wt) were an order of magnitude higher than in the blubber (48-320 ng/g wet wt). TBT was the predominant butyltin species in the blubber while DBT accounted for an higher proportion in the liver of dolphins. Butyltin concentrations in bluefin tuna were lower than those in dolphins, with TBT highest in the muscle and DBT in the liver. Concentrations of BTs in blue sharks were lower than those in dolphin and tuna, with kidney having the highest concentrations. TBT was the predominant form of butyltin derivatives in all the tissues of shark. Accumulation of butyltin compounds in liver/kidney seems to be associated with the presence of proteins such as glutathione.

Mercury concentrations in hair from populations in Wau-Bulolo area, Papua New Guinea.

Total mercury (Hg) concentrations were determined in scalp hair from the populations in the Wau-Bulolo area, eastern Papua New Guinea (PNG), where humans are exposed to large quantities of Hg through gold-mining activities by Hg amalgamation processes. Humans living upstream and not engaged in gold mining had a mean hair Hg concentration of 0.55 micro g g-1 (range: 0.19-1.1 micro g g-1 (n = 80), which was recognized as the background level in this area. In contrast, the populations involved in gold-mining activities had a significantly higher level of hair Hg (mean: 1.2 micro g g-1, range: 0.39-3.0 micro g g-1 (n = 86) than the background level, indicating direct or indirect exposure to Hg from gold mining. The hair Hg level in populations downstream of the gold-mining area was significantly higher than the background level, due to the consumption of Hg-contaminated fish. Mercury concentrations were significantly higher in males than in females, regardless of location properties.

Metal accumulation in tissues of seabirds from Chaun, northeast Siberia, Russia.

Concentrations of four essential elements (Fe, Mn, Zn, and Cu) and two toxic metals (Cd and Hg) were determined in selected tissues of 11 seabird species collected in Chaun, northeast Siberia. In oldsquaw, arctic tern and herring gull, zinc concentrations were correlated with Cd concentrations. Cadmium concentrations in all the species were highest in kidney and Hg in liver. Cd levels in the liver and kidney of herring gulls were higher than those observed from other breeding areas. Similarly, Hg concentrations were also high in the liver of herring gull. High concentrations of Cd and Hg found in some birds from Chaun might have arisen from exposure on migration.

Specific accumulation of mercury and selenium in seabirds.

Total mercury (T-Hg), methyl mercury (MeHg) and selenium (Se) concentrations were determined to elucidate the relationship between Hg and Se levels in the liver of 10 seabird species. Highest concentrations of T-Hg (mean 267 microg/g dry wt), MeHg (mean 25.5 microg/g dry wt) and Se (mean 113 microg/g dry wt) were in the liver of black-footed albatross (Diomedea nigripes). An equivalent molar ratio of 1:1 between T-Hg and Se was found in the liver of individuals which contain over 100 microg Hg/g. However, such a relationship was unclear in other individuals which had relatively low Hg levels. This suggests that Se plays a role in Hg detoxification for those individuals with high Hg. In seabird tissues, Hg and Se levels should be a most important factor determining the relationship between Hg and Se, and fluctuation of Hg burden through molting and the species-specific demethylation capacity would also influence their relationships.

Trace element accumulation in Baikal seal (Phoca sibirica) from the Lake Baikal.

Trace element concentrations (Fe, Mn, Zn, Cu, Pb, Ni, Cd, Co and Hg) were determined in 60 Baikal seals and in fishes collected from Lake Baikal in 1992. Low levels of Hg and Cd were found in Baikal seals in comparison with those of marine mammals and it was due to their low concentrations in dietary fish. These results suggest that pollution by Hg and Cd was low in Lake Baikal and these toxic elements were unlikely to be the causative factors for mass mortality of Baikal seal in 1987-1988. Significant correlation of Hg concentration between hair and internal tissues suggested the use of hair for Hg monitoring in pinnipeds. Among essential elements, higher Fe and lower Cu levels were specifically found in the liver of Baikal seal. The noticeable accumulation of essential elements might be related to the unique and specific environment of Lake Baikal.

Isomer-specific analysis of polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in red fox and human adipose tissue from central Italy.

The general exposure of humans and foxes to polychlorinated biphenyls (PCBs) and DDT in Italy was determined by analysis of adipose tissue samples collected from 1991-1992. sigma PCB concentrations varied between 1.0 and 2.6 micrograms/g (wet wt.). sigma DDT concentrations ranged from 1.6 to 5.0 micrograms/g (wet wt.). About thirty-five PCB congeners were identified in most samples. PCB congeners of IUPAC Nos. 138, 153, and 180 were the most abundant compounds, accounting for an average of 50% of the sigma PCBs in humans and 64% in foxes. Generally, higher chlorinated biphenyls and those with a 2,4,5-chlorine substitution in one ring and at least one substitution in the 4-position of the other ring were preferentially accumulated. Coplanar PCB congeners were detected at considerable concentrations and there is no sign of decline in their concentrations with respect to previously reported data. IUPAC Nos. 118, 156 and 126 were the main contributors to toxicity in humans and foxes. The significant contribution of mono-ortho congeners in humans and non-ortho congeners in foxes suggests that differences in metabolic potential may affect the PCB toxicity pattern.

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries.

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.