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.     

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.     

Mercury,organic-mercury and selenium in small cetaceans in Taiwanese waters

Total Hg (∑Hg), organic-Hg (O-Hg) and Se bioaccumulations in small cetaceans distributed in Taiwanese waters of the Taiwan Strait and the southwestern Pacific have been investigated for the first time. The results could represent the baseline metal concentrations of marine mammals in the southwestern Pacific, where volcanic activities are possibly the major source of mercury to the environments. Muscle samples of four species of small cetaceans were collected from animals accidentally caught by tuna-longline fisheries from 1994 through 1995. In total, 53 pantropical spotted dolphins, Stenella attenuata, nine spinner dolphins, S. longirostris, five bottlenose dolphins, Turiops truncatus and four Risso's dolphins, Grampus giseus were analyzed. In addition, two stranded pantropical spotted dolphins were investigated. Cold vapour AAS and ICP-MS were used in the analysis of Hg and Se, respectively. Significant species difference was found in the four species of small cetaceans. Among them, the pantropical spotted dolphin showed the highest mean concentration (mg/kg wet wt.) of both ∑Hg (3.64±2.19) and O-Hg (2.79±1.23), whereas the Risso's dolphin had the highest mean concentrations of Se (1.77±1.29). There was no significant sex difference with respect to metal bioaccumulation in the samples of S. attenuata. Significant correlations between body length (BL) and ∑Hg, as well as O-Hg concentrations were observed in pantropical spotted (Sa) and spinner dolphins (Sl). The linear relationships were Sa: ∑Hg=−8.290+0.066BL, r=0.421; Sl: ∑Hg=−2.735+0.025BL, r=0.875; Sa: O-Hg=−3.723+0.036BL, r=0.408; and Sl: O-Hg=−3.017+0.025BL, r=0.870. However, a demethylation phenomenon that decreasing the percentage of O-Hg coupled with increasing levels of Se was observed when the ∑Hg concentrations in the muscle tissues of dolphins reached 4 mg/kg wet wt.     

New insights from age determination on toxic element accumulation in striped and bottlenose dolphins from Atlantic and Mediterranean waters

This study aimed at comparing toxic element (Hg, Cd) bioaccumulation in relation to age for bottlenose (Tursiops truncatus) and striped dolphins (Stenella coeruleoalba) from Mediterranean and Atlantic waters. Metal concentrations were also measured in selected prey to infer metal exposure through the diet. As expected, Mediterranean prey exhibited the highest Hg levels, probably as a consequence of the Hg enrichment of the Mediterranean Sea. Comparing the predators from each area and taking age into account, Mediterranean bottlenose dolphins displayed higher Hg levels than Atlantic dolphins (p = 0.032), whereas Mediterranean striped dolphins did not (p = 0.691). The consumption of Myctophid fish, which showed the highest Hg levels (105+/-80 ngg(-1) w.wt.) among Atlantic prey, may explain the high Hg levels in the liver of the Atlantic striped dolphins and suggested a preferential offshore feeding behaviour in this area. Concerning Cd, no clear differences were found between geographical areas.     

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.     

Investigating the presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean sea

The presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean, Spain, is investigated. These pollutants were determined in white and red muscle and liver by gas chromatography coupled to tandem mass spectrometry. Contaminant profiles present in both wild and farmed fish tissues include DDTs, PCBs and HCB. The highest concentrations of contaminants were found in liver, and an increase in pollutant levels was observed in autumn, before spawning. This fact is explained in light of increased food intake when sea water temperatures increase. Gilthead sea bream from Western Mediterranean populations showed significantly higher concentrations of DDTs and PCBs than farmed fish from the same area. This fact is attributed to the low level of organochlorine contaminants present in fish feed supplied to the cultured fish. The diet is highlighted as an important factor in understanding differences observed in organochlorine pollutants levels of fish tissues.     

Assessment of perfluorinated compounds (PFCs) in plasma of bottlenose dolphins from two southeast US estuarine areas: relationship with age, sex and geographic locations

Plasma PFCs were measured in 157 bottlenose dolphins (Tursiops truncatus) sampled from two US southeast Atlantic sites (Charleston (CHS), SC and Indian River Lagoon (IRL), FL) during 2003-2005. ∑PFCs, perfluoroalkyl carboxylates (∑PFCAs), perfluoroalkyl sulfonates (∑PFSAs) and individual compounds were significantly higher in CHS dolphins for all age/sex categories compared to IRL dolphins. Highest ∑PFCs concentrations occurred in CHS juvenile dolphins (2340 ng/g w.w.); significantly higher than found in adults (1570 ng/g w.w. males; 1330 ng/g w.w. females). ∑PFCAs were much greater in CHS dolphins (≈ 21%) compared to IRL dolphins (≈ 7%); ∑PFSAs were 79% in CHS dolphins versus 93% in IRL dolphins. PFOS, the dominant compound, averaged 72% and 84%, respectively, in CHS and IRL dolphins. Decreasing PFC levels occurred with age on the bioaccumulation of PFCs in both sites. These observations suggest PFC accumulation in these two dolphin populations are influenced by site-specific exposures with significantly higher levels in CHS dolphins.     

Organochlorine and heavy metal concentrations in blubber and liver tissue collected from Queensland (Australia) dugong (Dugong dugon)

Tissue samples of liver and blubber were salvaged from fifty-three dugong (Dugong dugon) carcasses stranded along the Queensland coast between 1996 and 2000. Liver tissue was analysed for a range of heavy metals and blubber samples were analysed for organochlorine compounds. Metal concentrations were similar in male and female animals and were generally highest in mature animals. Liver concentrations of arsenic, chromium, iron, lead, manganese, mercury and nickel in a number of individual animals were elevated in comparison to concentrations previously reported in Australian dugong. Dieldrin, DDT (and its breakdown products) and/or heptachlor epoxide were detected in 59% of dugong blubber samples. In general, concentrations of organochlorines were similar to those reported in dugong 20 years earlier, and were low in comparison to concentrations recorded from marine mammal tissue collected elsewhere in the world. With the exception of lead, the extent of carcass decomposition, the presence of disease or evidence of animal starvation prior to death did not significantly affect dugong tissue concentrations of metals or organochlorines. The results of the study suggest that bioaccumulation of metals and organochlorine compounds (other than dioxins) does not represent a significant risk to Great Barrier Reef dugong populations, particularly in the context of other pressures associated with coastal development and other anthropogenic activities.     

Contamination and toxic effects of persistent endocrine disrupters in marine mammals and birds

In recent years, several species of marine mammals and birds have been affected by uncommon diseases and unusual mortalities. While several possible causative factors have been attributed for these events, a prominent suspect is exposure to man-made toxic contaminants. Particularly, some of these man-made chemicals can disrupt normal endocrine physiology in animals. At CMES, our studies focus on exposure and toxic effects of endocrine disrupting chemicals, particularly organochlorines, in higher trophic level wildlife. Endocrine disrupting chemicals, such as organochlorine insecticides, polychlorinated biphenyls, organotins etc. are found in tissues of a wide variety of wildlife. Extremely high concentrations have been found in animals afflicted with diseases and/or victims of mass mortalities. Elevated contamination by organochlorines has been found in open sea animals such as cetaceans and albatrosses, which seemed to be attributable to their low capacity to metabolize toxic persistent contaminants. Significant correlations between biochemical parameters (serum hormone concentrations and cytochrome P450 enzyme activities) and residues of endocrine disrupting chemicals were found in some species of marine animals, which indicates that these chemicals may impose toxic effects in animals even at the current levels of exposure. In general, water birds and marine mammals accumulated the dioxin-like compounds with much higher concentrations than humans, implying higher risk from exposure in wildlife. The future issues of endocrine disrupting chemicals in humans and wildlife will have to be focused in developing countries.     

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.     

Contaminant concentrations, biochemical and hematological biomarkers in blood of West Indian manatees Trichechus manatus from Brazil

The West Indian manatee Trichechus manatus is threatened with extinction in Brazil, and this study focused on nondestructive blood samples analyzed for metals, polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), as well as biochemical and hematological biomarkers. Studied manatees were kept at Projeto Peixe-Boi headquarters in Pernambuco State, and at two natural areas in estuaries where they are released to the wild. Manatees kept at the natural estuary in Paraiba State have blood concentrations of Al, Pb, Cd, Sn that are 11, 7, 8 and 23 times greater, respectively, than the concentrations found in blood of animals from the same species in Florida, USA. An inhibition of butyrylcholinesterase in manatees kept at the two reintroduction sites in Alagoas and Paraiba States indicated possible exposure of the animals to cholinesterase inhibitor insecticides. PCBs and OCPs were not detected. Results from this study will help delineate conservation efforts in the region.     

Perfluorinated compounds in minke whales (Balaenoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) from Korean coastal waters

This is the first study to report the concentrations and accumulation profiles of PFCs in marine mammals from Korea. The concentrations and profiles of 10 PFCs in the liver of minke whales and common dolphins from Korean coastal waters were recorded in this study. The mean concentrations of PFOS and PFUnDA were 3-20 times higher than that found for other PFCs analyzed. The concentrations of PFOS in cetaceans from Korea were relatively lower than those reported in other countries. Inter-species differences in the concentrations of PFOS, PFOSA and PFNA were found between two cetacean species, while no difference was observed in the concentrations of PFDA, PFUnDA and PFDoDA between the species. The dominant PFC compounds found in cetaceans were PFUnDA and PFOS, accounting for 70-80% of the PFCs. The accumulation profiles and correlation analysis indicated that two cetacean species have different exposure routes and metabolic capacity for PFCs.     

Concentrations and hazard assessment of polychlorinated biphenyls and organochlorine pesticides in shark liver from the Mediterranean Sea

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (DDTs), were determined in the liver of two different shark species Prionace glauca (blue shark) and Dalatias licha (kitefin shark) from the Mediterranean Sea. In blue shark liver, the concentrations of PCBs (2482 ngg(-1)) and DDTs (2392 ngg(-1)) were comparable, while in kitefin shark the hepatic concentrations of DDTs (4554 ngg(-1)) were significantly higher than those of PCBs (1827 ngg(-1)). Contamination levels differed between species, with kitefin shark showing consistently higher concentrations of DDTs, and blue shark higher levels of PCBs. Congener-specific PCB profiles, similar between the two species were dominated by the higher chlorinated congeners (hexachlorobiphenyls: 62.8-63.9%, penta-: 15.2-21.3%, hepta-: 13.4-14.5%) with most of the lower chlorinated congeners being absent or present at very low levels. In both species, the total 2,3,7,8-tetrachlorodibenz-p-dioxin toxic equivalent (TEQs) concentrations (blue shark: 2.51 pg/g; kitefin shark: 1.46 pg/g) seem to be relatively modest. Regards to DDT component pattern, p,p'-DDE was dominant in the liver of both species (blue shark: 81.5%; kitefin shark: 38.0%), while the percentage composition of the other metabolites was differently characterized. The composition pattern of DDTs and the low value of p,p'-DDE/DDTs ratio in the specimens from Ionian Sea suggest that organochlorine pesticide contamination is still continuing in this marine environment.     

Impacts of gold mine waste disposal on deepwater fish in a pristine tropical marine system

Little is known about the impacts of mine waste disposal, including deep-sea tailings, on tropical marine environments and this study presents the first account of this impact on deepwater fish communities. The Lihir gold mine in Papua New Guinea has deposited both excavated overburden and processed tailings slurry into the coastal environment since 1997. The abundances of fish species and trace metal concentrations in their tissues were compared between sites adjacent to and away from the mine. In this study (1999-2002), 975 fish of 98 species were caught. Significantly fewer fish were caught close to the mine than in neighbouring regions; the highest numbers were in regions distant from the mine. The catch rates of nine of the 17 most abundant species were lowest, and in three species were highest, close to the mine. There appears to be limited contamination in fish tissues caused by trace metals disposed as mine waste. Although arsenic (several species) and mercury (one species) were found in concentrations above Australian food standards. However, as in the baseline (pre-mine) sampling, it appears they are accumulating these metals mostly from naturally-occurring sources rather than the mine waste.     

Contaminants in cetaceans from UK waters: status as assessed within the Cetacean Strandings Investigation Programme from 1990 to 2008

Since 1990, tissue samples from UK-stranded and -bycaught cetaceans have been available for study of contaminant burdens. These have been used to study spatial and temporal trends in concentrations in UK waters, and to investigate potential associations between contaminants and health status. We describe the current status of cetaceans (primarily harbour porpoises, Phocoena phocoena) in UK waters in relation to pollution. Concentrations of BDEs, HBCD, and the organochlorine pesticides are declining. In contrast, concentrations of CBs have plateaued following earlier reductions due to regulation of use, and further reductions are likely to take decades. Blubber PCB concentrations are still at toxicologically significant levels in many harbour porpoises and regularly occur at even higher levels in bottlenose dolphins and killer whales due to their higher trophic level in marine food chains. Further reductions in PCB inputs into the marine environment are needed to mitigate risk from PCB exposure in these species.     

Chlorinated compounds and polybrominated diphenyl ethers (PBDEs) in mussels (Mytilus galloprovincialis) collected from Apulia Region coasts

This project was carried out to assess the levels and spatial distribution of organochlorine compounds in the coastal marine environment, using mussels as bioindicators to evaluate the coastal water quality. Levels of polychlorobiphenils (PCB), chlorinated pesticides (DDT isomers, HCH isomers, Aldrin, Dieldrin, alfa-Endosulfan, Hexachlorobenzene, Pentachlorobenzene) and polybrominated diphenyl ethers (PBDEs) were determined in tissues from mussels (Mytilus galloprovincialis) collected along the Apulia Region coasts (Mediterranean Sea). Results indicate that contamination by organochlorine compounds is higher in mussels sampled in the Ionian Sea than in those from the Adriatic Sea, with PCB levels up to seven times higher in mussels from Ionian than from the Adriatic Sea. Although PCB levels were above the maximum values indicated by both European Community (EC) and National regulation in several sample sites, the PCB concentrations were particularly high in some stations, suggesting that these locations require a much specific attention. Conversely, results on the mussel contamination by PBDEs highlight their ubiquitous environmental distribution, and underline the need to establish the maximum level for these compounds in foodstuff, according to European Regulations.     

Organohalogen contaminants in striped dolphins (Stenella coeruleoalba) from Japan: Present contamination status, body distribution and temporal trends (1978-2003)

Organohalogen contaminants including PCBs, DDTs, CHLs, HCHs, HCB, PBDEs and HBCDs were determined in striped dolphins (Stenella coeruleoalba) found stranded at Gogo-shima (n = 6, 2003) and collected from Taiji (n = 15, 1978-1992) in Japan. All target compounds were significantly detected in all the specimens, indicating ubiquitous contamination of oceanic cetaceans in northwest Pacific Ocean. Examination of body distribution of organohalogens in the six specimens from Gogo-shima showed no significant difference in concentrations among the analyzed tissues, except for brain, which had lower levels possibly due to the existence of blood-brain barrier. For evaluating temporal trends, archived blubber samples of adult male stripped dolphins collected in 1978, 1979, 1986 and 1992 were analyzed. Concentrations of PCBs, DDTs and HCHs did not change significantly during 1978-2003. In contrast, remarkable increasing trends of PBDEs and HBCDs were observed, suggesting growing consumption in Japan and surrounding countries in recent years.     

Trace metals in tissues of gray whale (Eschrichtius robustus) carcasses from the Northern Pacific Mexican Coast

Samples of liver, lung, heart, muscle, and blubber tissue from the carcasses of juvenile gray whales (Eschrichtius robustus) found stranded on the coast off the Sea of Cortez, México were analyzed for a range of trace metals (Cu, Fe, Zn, Mn, Ni, Pb, and Cd). The highest concentrations of copper, iron, zinc, and manganese were found in liver; nickel and lead in heart, and cadmium in kidney. In all tissues analyzed, iron, zinc and copper were present in the highest concentrations; however, some whales also showed high levels of cadmium in the kidney which could be related to their diet. Elevated concentrations of copper were found only in the liver of one whale. In general, where low levels of iron were found in the liver, they were associated with poor nutrition. Lead, nickel, manganese and zinc levels in liver were within the normal range, indicating that these whales had not been exposed to high levels of these metals.     

Organochlorine pollution in sperm whales,Physeter macrocephalus,from the temperate waters of the eastern North Atlantic

Residues of DDE, DDD, DDT and PCB were measured in different tissues of fourteen sperm whales caught in the waters off Spain's north-western coasts. Unlike what seems common in other marine mammal species, females appear to be more contaminated by organochlorine compounds than males. Pollutant levels in this species were found to be intermediate to other cetaceans, probably due to their feeding habits mainly based on squid and bottom fish. Concentrations of total DDT and PCB in blubber were similar to most of those determined in sperm whales from other areas of the northern hemisphere.     

Sweden

Four invertebrate and one fish species (Cerastoderma edule, Mya arenaria, Arenicola marina, Crangon crangon, Solea solea) from a single area of the German Wadden sea were investigated for concentrations of ten organochlorine pollutants in 1976. PCB concentrations (wet tissue basis) were predominating with 10–200 ng g^?1, while p,p′-DDD, dieldrin, α-HCH, γ-HCH and p,p′-DDE generally ranged between 1 and 10 ng g^?1. Values of α-endosulfan were even lower; p,p′-DDT, endrin and heptachlor epoxide could not be detected. Residue levels in shrimps were close to the lower range of values which have been found in this species from other areas of the North Sea since 1974. The patterns of residue concentrations in the five aquatic species were remarkably different indicating species- and compound-specific bioaccumulation. Trophic level and lipid content were shown to be responsible for PCB concentrations increasing from bivalves to fish.