Polychlorinated biphenyl and organochlorine pesticide residues in Lophius budegassa from the Mediterranean Sea (Italy)

Persistent organochlorines, such as polychlorinated biphenyls, including coplanar congeners and DDT compounds, were measured in the liver of a teleost species: namely, Lophius budegassa. The mean concentrations of PCBs (1249 ng/g wet wt) were comparable with DDTs mean levels (1459 ng/g wet wt). Among DDTs the compound found at the highest concentration was p,p'-DDE representing 76% of the total DDT burden. The PCB profiles were dominated by congeners 153, 180, and 138 accounting for 49.8%, 16.0% and 13.7% of the total PCBs. The total 2,3,7,8-TCDD toxic equivalent (TEQs) of six coplanar PCBs, including mono- and non-ortho congeners, was 0.98 pg/g wet wt. The congeners with highest TEQs values were non-ortho-congeners followed by mono-ortho ones.     

Contamination by Persistent Organochlorines in Small Cetaceans from Hong Kong Coastal Waters

Blubber samples of 2 cetacean species, the Indo-Pacific hump-backed dolphin (Sousa chinensis) (n=11) and finless porpoise (Neophocaena phocaenoides) (n=9), collected from Hong Kong coastal waters were analysed for persistent organochlorines. Mean concentration in the blubber of DDTs was ranked first (46 μg/g wet wt.), followed by PCBs (24 μg/g wet wt.), HCHs (0.76 μg/g wet wt.), chlordane compounds (0.38 μg/g wet wt.) and HCB (0.07 μg/g wet wt.). The present cetacean species may potentially be faced with high risk due to the elevated level of DDTs and PCBs. Relatively high concentrations of PCBs and DDTs can be attributed to the continuous environmental input of these compounds in the Far East region including Hong Kong. Highly chlorinated PCBs such as IUPAC Nos. 138, 153, 180 were the prominent congeners, accounting for 39% of the total PCBs. Mean concentrations of 6 non- and mono-ortho coplanar congeners were 2.1 and 2.8 μg/g wet wt. in the hump-backed dolphin and finless porpoise, respectively. Among highly toxic coplanar PCBs, mono-ortho congener IUPAC No. 118 and non-ortho congener IUPAC No. 126 were estimated to have the greatest toxicity contribution. Tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol (TCPMeOH), which have been the most recently identified microcontaminants, were also detected with the highest concentration of 290 and 300 ng/g (wet wt. basis), respectively. The concentrations of TCPMe relative to TCPMeOH in cetaceans from Hong Kong coastal waters were significantly higher than those found in various seals collected from other parts of the world, suggesting the different metabolic system of these two compounds between seals and cetaceans. Correlations between the concentrations of tris-chlorophenyl compounds with other persistent organochlorines such as HCHs, CHLs, DDTs and PCBs were significant, suggesting their accumulation nature similar to these organochlorines.     

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.     

Specific accumulation of persistent organochlorines in bluefin tuna collected from Japanese coastal waters

Concentrations of persistent organochlorines (OCs) such as PCBs, DDTs, chlordanes (CHLs), HCHs and HCB were determined in the liver of bluefin tuna (Thunnus thynnus) collected from Japanese coastal waters in order to elucidate accumulation profiles and to evaluate the suitability of this species as a biomonitor for pollution in the open sea ecosystem. Concentrations of PCBs, DDTs and CHLs in bluefin tuna increased significantly with body length (30–190 cm). HCHs and HCB residues were comparable among all the sampling regions, and the levels of these chemicals did not show correlation with body length. These results suggest significance of dietary uptake of PCBs, DDTs and CHLs compared to the intake via the gill. On the other hand, equilibrium partitioning with ambient water is a major determinant of the levels of HCHs and HCB in tuna. Body-length normalized values (BLNV) of PCBs, DDTs and CHLs concentrations in bluefin tuna were calculated using the linear regression equation obtained from the plot of concentrations and body length. BLNV of these chemicals on a lipid wt basis, which was adjusted for 100 cm body length, were indicative of the present state water pollution by PCBs, DDTs and CHLs. These results suggest that bluefin tuna is a suitable bioindicator for monitoring OCs contamination in the open sea ecosystem.     

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.     

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.     

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.     

Horizontal and vertical distribution of PCBs and chlorinated pesticides in sediments from Masan Bay,Korea

Horizontal and vertical distributions of organochlorine compounds (OCs) were determined in sediments from Masan Bay. The concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs), HCB, hexachlorocyclohexanes (HCHs) and chlordane related compounds (CHLs) in sediments were in the range of 1.24-41.4, 0.28-89.2, 0.02-0.59, nd-1.03, and nd-2.56 ng/g, respectively. The spatial distribution of OCs showed a negative gradient from the inner of the bay to outer part of the bay, indicating that the source of OCs was probably located inside the bay. Compositional pattern of PCB congeners showed a relatively high concentration of high-chlorinated congeners in the inner part of the bay and a relatively low concentration of low-chlorinated congeners in the outer part. In sediment core from Masan Bay maximum concentrations of PCBs and DDTs are observed in the subsurface samples and correspond to an age of early 1980s and late 1960s. The concentration profiles of PCBs and DDTs in sediments of Masan Bay appear to correspond to use of PCBs and DDTs in Korea.     

Chlorinated hydrocarbons in marine fish and shellfish of Nigeria

The concentration ranges of chlorinated hydrocarbons in marine fish were HCB (0.03–9.5 ppb), Lindane (0.02–5.3 ppb), Endosulphan (0.21–4.9 ppb), DDT (0.50–18.6 ppb), Aldrin (0.05–54.6 ppb) and PCB (4.78–225 ppb). Fish contained higher concentrations of Aldrin, Heptachlor, HCB and Lindane than shellfish, while a reverse trend was observed for DDT and PCBs. The concentrations of residues obtained were found to be lower than those reported in literature for industrialized countries. Predator fish species were found to concentrate more residues in muscle tissue than plankton feeders. The DDT/PCB values were less than 1 indicating a predominance of industrial activities over agricultural activities as the source of contamination of the marine environment. The fish Galeoides decadactylus is a potential bio-indicator for chlorinated hydrocarbons pollution monitoring in the study area.     

Organochlorines in Hong Kong Fish

Muscle samples from 15 species of fish (n=1) purchased from markets in Hong Kong and 10 liver samples of tilapia (Tilapia mossambica) collected from the Shing Mun River were analysed for organochlorines (polychlorinated biphenyls, ΣDDTs, hexachlorobenzene, hexachlorocyclohexanes, chlordanes, mirex and dieldrin). Polychlorinated biphenyls (PCBs) were detected in 15 market fish samples but the levels were very low (around 1 ng g⁻¹). PCB levels in tilapia livers collected from Tai Wai (29.3–65.1 ng g⁻¹) were higher than those from Fo Tan (3.5–23.2 ng g⁻¹) suggesting that there may be some local point soucres. ΣDDTs were detected in all samples, ranging from 3.3 to 75.6 ng g⁻¹ in the market fish and from 7.1 to 88.8 ng g⁻¹ in tilapia. The DDE/DDT ratios in the market fish (0.12–0.75) showed higher variability than those of tilapia (0.30–0.46), suggesting that some of the market fish may have been collected from areas where DDT was recently used. Results of this preliminary study show that organochlorine levels in Hong Kong market fish are low and do not cause any concern for human consumption. An on-going monitoring program, however, is recommended.     

Organohalogen and organotin compounds in killer whales mass-stranded in the Shiretoko Peninsula, Hokkaido, Japan

Blubber and liver samples were obtained for analysis of wide ranges of contaminants from killer whales (Orcinus orca) which were locked away in drifting sea ice on the coast of Rausu, the Shiretoko Peninsula in Eastern Hokkaido, Japan in February 2005. Among the organohalogen compounds analyzed, DDTs were the predominant contaminants with concentrations ranging from 28 to 220 microg/g on a lipid-weight basis followed by PCBs and other organochlorine pesticides. PBDEs levels were two or three orders of magnitude lower than those of PCBs and DDTs. 2,3,7,8-Tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) derived by WHO mammal-TEF in killer whales were in the range of 110-440 pgTEQ/g. Mono-ortho coplanar PCBs contributed to 75-98% of total TEQs, indicating coplanar PCBs are significant contaminants for risk assessment in this species. The fact that hepatic residue levels of butyltins (from 13 to 770 ng/g wet weight) were much higher than those of phenyltins may be reflecting extensive use of tributyltin as antifouling paint.     

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.     

Deposition of semi-volatile organochlorine compounds in the free troposphere of the eastern North Atlantic Ocean

Deposition samples were taken at a height of 2367 m above sea level (m.a.s.l.) on the Island of Tenerife from May 1999 until July 2000 and analysed for 19 polychlorinated biphenyl (PCB) congeners, hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH) and DDTs. This site is located above the inversion layer, so samples represent background concentrations of the free troposphere. The average deposition fluxes of HCB, total HCH, DDTs and PCBs were 86, 400, 110 and 780 ng m(-2) yr(-1), respectively, being lower than those reported at sea level in continental or marine areas. All compounds are generally found in higher abundance in the wet precipitation samples. However, these samples only represent a fraction, e.g. 33%, of the total deposition load. Annual mass balance calculations show that wet precipitation is essentially responsible for the deposition of the low molecular weight OC whereas dry deposition accounts for more than 50% of the higher molecular weight PCBs.     

Levels of organochlorine pesticide residues in some organs of the Ganges perch, Lates calcarifer, from the Ganges-Brahmaputra-Meghna Estuary, Bangladesh

Levels of organochlorine pesticide residues (p,p′ DDT, DDD, DDE, Aldrin, Dieldrin, Lindane, Heptachlor and BHC) were analysed in the dry and wet seasons in four organs (muscle, liver, gut and egg samples) of Ganges Perch, Lates calcarifer, collected during October–November–December, 1996 and May–June–July, 1997 from the Ganges–Brahmaputtra–Meghna estuary. The residues were analysed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). Among the four organs analysed, the residues were found in the order egg > gut > muscle > liver. The pesticide residues were found in the order ∑DDT > Heptachlor >Dieldrin > Aldrin. Higher levels of residues were found during the dry season due to high lipid content in fishes. A positive correlation was observed between the pesticide residues (∑DDT and ∑OCs) and lipid contents of fish, and the correlation was found to be linear. The concentrations of pesticide residues in muscle, liver and gut were below the FAO/WHO (1993) recommended permissible limit except in eggs.     

Contamination by persistent organochlorines and butyltin compounds in the west coast of Sri Lanka

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), isomers of hexachlorocyclohexane (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and butyltin compounds (mono-, di- and tributyltin) were determined in biota and sediments collected from locations on the west coast of Sri Lanka. The PCB concentrations found in fish from the Kelani River mouth were higher than those from other Asian developing countries. The pattern of organochlorine accumulation was in the order of PCBs > DDTs > CHLs > HCHs > HCB, and resembled those reported for most developed countries. The accumulation pattern of butyltins in fish was in the order of TBT > DBT > MBT suggesting recent exposure to TBT sources. Total butyltin concentrations found in rabbit fish liver (11-38 micrograms/g wet wt), collected from the Colombo dockyard, could be the highest ever reported for fish in the world.     

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.     

Organochlorine pesticides and PCB residues in sediments of Alexandria Harbour,Egypt

Persistent organochlorine compound concentrations were determined for 23 surface sediment samples collected from Alexandria Harbor, Egypt. Total PCB concentrations ranged from 0.9 to 1210 ng/g with four to seven Cl-substituted biphenyls being the most prevalent PCBs congeners. Different PCB congener distribution patterns were observed, probably reflecting different inputs and attenuation at various locations. Total DDT concentrations varied from <0.25 ng/g to 885 ng/g. The ratios of DDTs (2,4^′- and 4,4^′-DDT)/total DDTs (DDTs plus metabolites) in sediment samples from certain sites were 0.86 or higher, indicating little attenuation or recent input of DDT. Total chlordane (the sum of heptachlor and its epoxide, oxy-, γ- and -chlordane and cis+trans-nonachlor) ranged from <0.25 to 44 ng/g with the highest concentration found in the Arsenal Basin. The geographic distributions of PCBs, total DDTs and total chlordane were similar. Chlorinated benzenes (CBs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin, endrin, chloropyrifos, endosulfan, mirex and pentachloroanisole were below detection limits or detected at low concentrations in most of the samples. Sites that were contaminated with high concentrations of organochlorine compounds were associated with dense population and low energy environment. The contamination levels of PCBs, total DDTs and total chlordane were in high range compared to other locations worldwide.     

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.     

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.