Concentrations of organochlorines in sperm whales (Physeter macrocephalus) from Southern Australian waters

Concentrations of DDTs, PCBs and HCHs were measured in sperm whales involved in two mass stranding events on the west coast of Tasmania, Australia in February 1998. DDTs and PCBs were present in all samples analysed, while only three contained HCHs. The relationships between organochlorines, sex, age and reproductive groups were marked by high variability. Differences in organochlorine concentrations were observed between animals from the two stranding sites and discussed in light of the ecology of this species. Concentrations of all pollutants were stratified throughout the vertical aspect of the blubber and possible reasons for and the implications of this are discussed. Concentrations of compounds were higher than those documented in this species in the Southern Hemisphere previously, although were relatively lower than those documented in the Northern Hemisphere. However, comparisons were confounded by spatial and temporal differences. Continued monitoring of marine mammals throughout this region in a co-coordinated, standardized manner is essential for establishing definite temporal and spatial variations in pollutant concentrations.     

Organochlorine contaminants in endangered Hawaiian monk seals from four subpopulations in the Northwestern Hawaiian Islands

We analyzed blubber and blood samples for organochlorines (OCs) from 158 Hawaiian monk seals (Monachus schauinslandi) at four of their six primary breeding colonies in the Northwestern Hawaiian Islands. Levels of OCs in blubber were lower in adult females compared to juveniles or adult males, evidently owing to the transfer of these lipophilic compounds to pups by pregnant and lactating females. Concentrations of SigmaPCBs and p,p'-DDE in blubber generally increased with age until seals were sexually mature and then continued to increase with age in males after puberty. Average levels of PCBs and PCB toxic equivalents (TEQs) in blubber were significantly higher in adult male and juvenile seals at Midway Atoll than the same age class of seals at the other colonies. Unlike concentrations of OCs in blubber, circulating levels of OCs in blood did not vary consistently among age classes of seals or among breeding colonies. Though the concentrations of OCs measured in Hawaiian monk seals were generally equal to or lower than those reported for other pinniped species in the North Pacific Ocean, they were high enough in a few seals to potentially affect their health.     

Metals and organochlorines in dolphins and porpoises of Cardigan Bay,West Wales

Concentrations of seven metals (Cr, Ni, Cu, Zn, Cd, Hg, and Pb) and a range of organochlorine pesticides, individual chlorobiphenyl congeners, and total polychlorinated biphenyls (PCB) have been determined in tissues of dolphins, porpoises, seals, and a variety of food chain species and sediments from Cardigan Bay, West Wales. Elevated concentrations of metals were not seen in any of the animal tissues examined. Higher than expected levels of organochlorine compounds were found in tissues of dolphins and porpoises; these concentrations are not derived from local pollution, but come from the animals' normal diet which did not show markedly elevated levels of organochlorines. The level of organochlorine bioaccumulation seen in some of the cetaceans analysed is much higher than found previously; this may have serious health implications for populations of those species around the coasts of NW Europe.     

Metal tissue levels in Steller sea lion (Eumetopias jubatus) pups

The endangered Western population of the Steller sea lion declined for three decades for uncertain reasons. We present baseline data of metal concentrations in pups as a first step towards investigating the potential threat of developmental exposures to contaminants. Seven metals were investigated: arsenic, cadmium, silver, aluminum, mercury, lead and vanadium. Vanadium was detected in only a single blubber sample. Mercury appears to be the most toxicologically significant metal with concentrations in the liver well above the current action level for mercury in fish. The concentrations of aluminum, arsenic, silver, cadmium and lead were present in one-fourth to two-thirds of all samples and were at either comparable or below concentrations previously reported. Neither gender nor region had a significant effect on metal burdens. Future work should consider metal concentrations in juveniles and adults and toxicological studies need to be performed to begin to assess the toxicity of these metals.     

Polychlorinated biphenyls and chlorinated pesticides in harbor seals (Phoca vitulina concolor) from the northwestern Atlantic coast

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordane-related compounds (CHLs), mirex, hexachlorocyclohexane isomers (HCHs), dieldrin, and hexachlorobenzene (HCB) were determined in blubber of harbor seals (Phoca vitulina concolor) from the northwestern Atlantic coast. PCBs, DDTs, and CHLs were the major persistent organochlorines in harbor seal blubber, while mirex, HCHs, dieldrin, and HCB were minor contaminants. Highest concentrations were found in the adult males, followed by the pups, yearlings, adult females, and fetuses. DDT and PCB concentrations have declined from the high levels reported in the early 1970s, but no declines were observed in our samples over the ten-year period 1991-2001. DDT/PCB ratios were indicative of a more rapid decline of DDTs than PCBs, while ratios of p,p'-DDE/DDT were indicative of a metabolic "weathering" of DDT. The population appears to be susceptible to disease outbreaks, as evidenced by a recurrence of viral epizootics since the late 1970s. The PCB burdens in these seals are similar to levels reported in seals from polluted regions of Europe and Asia, and exceed the estimated threshold levels for adverse reproductive and immune system effects in the species.     

Organochlorine compound and trace metal contaminants in fish near Sydney's ocean outfalls

Sydney's inshore sewage outfalls were significant contributors to organochlorine contamination of inshore sedentary fish such as red morwong. Diversion of the sewage to deepwater outfalls has resulted in marked declines in the concentrations of these compounds in inshore red morwong. Apart from lead, however, similar trends did not occur for concentrations of trace metals. A wide variety of trace metals and organochlorine compounds were found in the flesh and/or livers of a variety of fish species caught at sites associated with the present deepwater ocean outfalls off Sydney. Fish caught at locations remote from Sydney also contained a wide variety of trace metals although organochlorine compounds were usually at lower levels. The mean contaminant levels in all species of offshore fish were generally found to be low when compared to the Australian National Food Authority's Maximum Residue Limit (NFA MRL). No fish analysed was found to have levels of an organochlorine compound above the MRL and no fish was found to have levels of zinc or lead above the MRL. When detected, fish with levels of a trace metal above the MRL appeared to be distributed throughout New South Wales, independent of the deepwater ocean outfalls off Sydney. There is no evidence as yet that the commissioning of the deepwater outfalls has led to an increase in levels of contaminants in the fish examined to the extent that they are of concern relative to the NFA MRLs.     

Using blood samples to estimate persistent organic pollutants and metals in green sea turtles (Chelonia mydas)

Persistent organic pollutants (POPs) and heavy metals have been reported in a number of green turtle (Chelonia mydas) populations worldwide. However, due to ethical considerations, these studies have generally been on tissues from deceased and stranded animals. The purpose of this study was to investigate the use of blood samples to estimate the tissue contamination of live C. mydas populations. This study analysed 125 POP compounds and eight heavy metals in the blood, liver, kidney and muscle of 16 C. mydas from the Sea World Sea Turtle Rehabilitation Program, Gold Coast, Australia. Strong correlations were observed between blood and tissue concentrations for a number of POPs and metals. Furthermore, these correlations were observed over large ranges of turtle size, sex and condition. These results indicate that blood samples are a reliable non-lethal method for predicting chemical contamination in C. mydas.     

Polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Hong Kong waters: levels, profiles and distribution

Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber, liver and kidney of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) stranded in Hong Kong coastal waters during 1995–2001. Among the organohalogen compounds analyzed, DDTs were the most dominant contaminants with concentrations ranging from 9.9 to 470 μg/g lipid wt. PBDEs in Hong Kong cetaceans, which are reported for the first time, were detected in all the samples with values ranging from 0.23 to 6.0 μg/g lipid wt., with a predominance of BDE-47. Results from this study suggest PBDEs should be classified as priority pollutants in Asia. Higher concentrations were found in humpback dolphins than in finless porpoises, and this was attributed mainly to differences in habitat. Elevated residues of PCBs and DDTs in some cetaceans suggest these species may be at risk.     

Patterns and Levels of Organochlorines (DDTs, PCBs, non-ortho PCBs and PCDD/Fs) in Male Harbour Porpoises (Phocoena phocoena) from the Baltic Sea, the Kattegat-Skagerrak Seas and the West Coast of Norway

Patterns and levels of chlorinated aromatic contaminants (DDTs, PCBs, non-ortho PCBs and PCDD/Fs) in blubber tissue were compared among six sample groups of male harbour porpoises (Phocoena phocoena) from the Baltic Sea, the Kattegat-Skagerrak Seas and the west coast of Norway. A principal component and classification analysis showed that mature harbour porpoises from the Baltic had significantly different contaminant patterns than animals from the Kattegat-Skagerrak and Norway. ANOVAs showed that mature porpoises from the Baltic had higher levels of ΣPCB and several individual PCBs and PCDD/Fs than the Kattegat-Skagerrak and the Norwegian samples and higher ΣDDT than the Norwegian. A comparison between immature porpoises showed that Baltic animals had higher levels of ΣPCDD/F than the corresponding sample from the Kattegat-Skagerrak. The levels of ΣDDT, ΣPCB and Σnon-ortho PCB were significantly higher in animals collected during 1978–81 compared to animals collected in 1988–90 indicating a temporal decline of these organochlorines in the Kattegat-Skagerrak Seas. The contaminant levels recorded in the Baltic Sea are a serious cause for concern and could have management implications for the already threatened harbour porpoises in this area.     

The use of a non-lethal tool for evaluating toxicological hazard of organochlorine contaminants in Mediterranean cetaceans: new data 10 years after the first paper published in MPB

In the Mediterranean Sea, top predators, and particularly cetacean odontocetes, accumulate high concentrations of organochlorine contaminants and toxic metals, incurring high toxicological risk. In this paper we investigate the use of the skin biopsies as a non-lethal tool for evaluating toxicological hazard of organochlorines in Mediterranean cetaceans, presenting new data 10 years after the paper published by Fossi and co-workers [Mar. Poll. Bull. 24 (9) (1992) 459] in which this new methodology was first presented. Some organochlorine compounds, now with worldwide distribution, are known as endocrine disrupting chemicals (EDCs). Here the unexplored hypothesis that Mediterranean cetaceans are potentially at risk due to organochlorines with endocrine disrupting capacity is investigated. High concentrations of DDT metabolites and PCB congeners (known as EDCs) were found in the different Mediterranean species (Stenella coeruleoalba, Delphinus delphis, Tursiops truncatus and Balaenoptera physalus). In this paper we also propose benzo(a)pyrene monooxygenase (BPMO) activity in marine mammal skin biopsies (non-lethal biomarker) as a potential indicator of exposure to organochlorines, with special reference to the compounds with endocrine disrupting capacity. A statistically significant correlation was found between BPMO activity and organochlorine levels (DDTs, pp(')DDT, op(')DDT, PCBs and PCB99) in skin biopsies of males of B. physalus. Moreover a statistical correlation was also found between BPMO activity and DDT levels in skin biopsies of the endangered Mediterranean population of D. delphis. These results suggest that BPMO induction may be an early sign of exposure to organochlorine EDCs and can be used for periodic monitoring of Mediterranean marine mammal toxicological status.     

Screening of Mercury and Persistent Organochlorine Pollutants in Long-Finned Pilot Whale (Globicephala melas) in the Faroe Islands

Results of mercury and organochlorine analyses in pooled muscle and blubber samples representing in all 417 long-finned pilot whales (Globicephala melas) sampled in 1997 in the Faroe Islands are presented. The 28 pooled muscle samples from (in all) 9 pods were analysed for total mercury and the same number of pooled blubber samples were analysed for PCB (IUPAC CBs no. 28, 52, 99, 101, 105, 118, 128, 138, 153, 170, 180, 183 and 187), p,p′-DDT and metabolites and o,p′-DDT and metabolites, cis () and trans (γ)-chlordane, cis- and trans-nonachlor, oxychlordane, mirex, hexachlorobenzene, β-HCH and toxaphene (Parlars no. 26 (T2), 32, 50 (T12), 62 (T20) and 69.     

Specific accumulation and temporal trends of organochlorine contaminants in Dall's porpoises (Phocoenoides dalli) from Japanese coastal waters

Organochlorine compounds (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane related compounds, hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol were determined in the blubber of Dall's porpoises (Phocoenoides dalli) collected from Japanese coastal waters in 1998/1999. Among OCs analyzed, PCBs were the predominant contaminants with concentrations ranging from 1.5 to 39 microg/g on a wet weight basis. OCs concentrations were relatively low and less variable in mature females possibly due to the lactational excretion from their bodies, while in males the concentrations were increased with body length. Concentrations and compositions of DDTs and HCHs showed significant differences between the truei-type population off the Pacific coast of northern Japan and dalli-type from the Sea of Japan/Okhotsk, suggesting its usefulness to discriminate different populations. OCs levels detected in truei-type porpoises collected in 1998/1999 were lower than those collected in 1984, except TCPMe. On the other hand, except DDTs, the residue levels of other organochlorines in dalli-type porpoises showed no significant decrease since 1984.     

Bioaccumulation and enantiomeric profiling of organochlorine pesticides and persistent organic pollutants in the killer whale (Orcinus orca) from British and Irish waters

Concentrations and enantiomeric profiles for a range of organochlorine compounds are reported in blubber samples from a number of individual killer whales (Orcinus orca) from British and Irish waters. Elevated contaminant levels and enriched isotopic ratios were determined in one individual whale sampled in the Scottish Western Isles compared to the others suggesting marine mammal based dietary influences. The potential application of isotopic ratios to model contaminant uptake, enantioselective enrichment and accumulation is demonstrated. Data are presented which provide information on enantioselective enrichment factors (EFs) for o,p'-DDT, alpha-HCH and toxaphene congeners CHB26 and CHB 50. This dataset further improves the current database on reported levels of a number of contaminants and provides additional background information on potential metabolic processes in killer whales from British and Irish waters.     

The role of organochlorines in cancer-associated mortality in California sea lions (Zalophus californianus)

Wild California sea lions (Zalophus californianus) have an unusually high prevalence of neoplasms (18% of stranded dead adults) and high levels of contaminants. The contribution of organochlorine (OC) tissue burdens to the probability of sea lions dying from carcinoma was explored using a logistic regression model. Levels of PCBs and DDTs were determined in blubber of sea lions diagnosed with metastatic carcinoma and animals that had died from non-carcinoma-related incidents (e.g., gunshot, domoic acid poisoning). Animals with carcinoma had higher mean concentrations (based on wet weight) of PCBs and DDTs (more than 85% and 30% higher, respectively) in blubber than did sea lions without carcinoma; the highest concentrations of OCs in the sea lions affected with carcinoma were measured in the males. Blubber thickness was significantly different between the two groups of sea lions, but after controlling for this difference, there was still a significant effect of PCBs, but not DDTs, on the probability of sea lions dying with carcinoma. Age, sex, mass and length did not affect the probability of dying from carcinoma.     

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.     

Contamination of Tris(4-Chlorophenyl) Methane and Tris(4-Chlorophenyl) Methanol in Marine Mammals from Russia and Japan: Body Distribution, Bioaccumulation and Contamination Status

Four seal species (Phoca caspica, Phoca sibirica, Phoca hispida and Phoca largha) and one whale (Orcinus orca) from Russia and Japan were examined to determine the body distribution, bioaccumulation and contamination status of tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol (TCPMOH). Lipid normalized concentrations of TCPMe and TCPMOH were comparable in various organs and tissues, implying that their body distribution is followed to the lipid-dependent accumulation, similar to that for other organochlorines. The highest body burden of these compounds was found in the blubber. Bioaccumulation potential of TCPMe and TCPMOH was high and comparable to PCBs and DDTs. Relatively higher concentrations of TCPMe and TCPMOH were observed in Caspian seal than in other seal species examined. TCPMOH concentration in killer whale was the highest of the marine mammals examined. Another peak detected had similar mass spectrum to TCPMOH, however, at a different retention time, suggesting the presence of an isomer of TCPMOH.     

Heavy metals,organochlorine pesticides and PCBs in green mussels,mullets and sediments of river mouths in Thailand

This investigation was undertaken to determine the levels of lead, zinc, copper, cadmium, and mercury and certain organochlorines including DDT and PCBs in green mussels, mullets, and bottom sediments of the mouths of the river Mae Klong, Ta Chin, Chao Phraya, and Ban Pakong. The four river mouths are contaminated by the five heavy metals to some extent. The contamination of lead in mussels, mullets and sediments was quite obvious, at values significantly higher than those previously reported. Contamination of the other four metals in mussels and mullets was still within acceptable limits, except for mercury in the Chao Phraya river mouth which was approaching the limit. Organochlorines, especially DDT and its metabolites, are detectable in some samples of mussels, mullet, and sediments. PCBs were detectable in some samples of mussels and mullets, but none were detected in the sediments. The levels of these organochlorines are considered to be comparable to baseline levels.     

Organochlorine compounds in tissues of swordfish (Xiphias gladius) from Mediterranean Sea and Azores islands

Polychlorobiphenyls (PCB) and organochlorine (OC) pesticides are endocrine-disrupting chemicals (EDCs). The Italian Ministry of Environment has undertaken a program (1999-2001) to measure levels of contaminants in top marine predators and to develop sensitive biomarkers for the evaluation of toxicological risk in these species. In 1999, 15 swordfishes (Xiphias gladius) taken from the Mediterranean Sea along the Sicilian coast (Strait of Messina, Italy) and in the Atlantic Ocean along the Azores Islands, and analysed for 34 congeners of PCBs and 27 organochlorine (OC) pesticides in gonad, muscle, liver and blubber tissues. In the tissues of Mediterranean swordfishes the sum of the determined PCBs congeners ranged from 4.61 to 4651.17 ng g(-1) on fresh tissue basis. Among organochlorine pesticides DDE, DDT and DDD (TDE) predominated with an overall range of 2.37-4734.56 ng(-1) w.w. In particular p,p'-DDE had concentrations appearing up to 3900 ng(-1), with the highest values found in fatty tissues, such as blubber. In the liver of Azores Island swordfishes lower levels of summation PCBs (8.43-294.17 ng/g w.w.) and summation DDTs (<0.01-217.44 ng/g w.w.) were determined.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay, Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p<0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Spatial aspects of organochlorine contamination in northern fur seal tissues

Northern fur seals from the Pribilof Islands, Alaska (St. George Is. and St. Paul Is.) were examined for organochlorine contamination (OC) and whether the organochlorine levels differed between the populations and were at levels that may adversely affect their health. Fur seal blubber and milk samples were obtained from pups, sub-adult males, and adult females on both Pribilof Islands. These samples were analyzed for organochlorine contaminants including dioxin-like PCBs and other selected PCBs and pesticides by high performance liquid chromatography/photodiode array. Results showed that there are clear differences between the two islands in the patterns of fur seal OC distribution. Generally, these differences are confined to the PCBs with only minimal differences in the DDTs. There are also clear biological differences in the levels shown between milk, pup blubber, and sub-adult male blubber. When considering blubber, St. George Is. fur seals show higher OC levels than St. Paul Is., for both pups and sub-adults. On the other hand, milk samples from St. Paul Is. showed higher PCB levels than St. George Is. For the milk, the overall OC levels may impact the immune function of the pups, but are probably of only minimal impact to humans. However, for blubber, the overall toxic equivalency shows levels exceeding those levels recommended for human consumption at St. George Is. and approaching those levels at St. Paul Is. The concentration curves suggest that the movement of OC in and out of milk follows a complex set of reactions dependent on how the OC compounds on a congener level are associated with lipid. In fact, there is some evidence that they may not follow the lipid as closely as we had thought and that lipid levels can vary without impacting the total OC level in the milk.