Accumulation of perfluorooctane sulfonate in marine mammals

Perfluorooctane sulfonate (PFOS) is a perfluorinated molecule that has recently been identified in the sera of nonindustrially exposed humans. In this study, 247 tissue samples from 15 species of marine mammals collected from Florida, California, and Alaskan coastal waters; and northern Baltic Sea; the Arctic (Spitsbergen); and Sable Island in Canada were analyzed for PFOS. PFOS was detected in liver and blood of marine mammals from most locations including those from Arctic waters. The greatest concentrations of PFOS found in liver and blood were 1520 ng/g wet wt in a bottlenose dolphin from Sarasota Bay, FL, and 475 ng/mL in a ringed seal from the northern Baltic Sea (Bothnian Sea), respectively. No age-dependent increase in PFOS concentrations in marine mammals was observed in the samples analyzed. The occurrence of PFOS in marine mammals from the Arctic waters suggests widespread global distribution of PFOS including remote locations.     

Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals,fishes, and birds from coasts of the Baltic and the Mediterranean Seas

Perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were detected in 175 samples of liver and blood of bluefin tuna (Thunnus thynnus), swordfish (Xiphias gladius), common cormorants (Phalacrocorax carbo), bottlenose dolphins (Tursiops truncatus), striped dolphins (Stenella coeruleoalba), common dolphins (Delphinus delphi), fin whales (Balenoptera physalus), and long-finned pilot whales (Globicephala melas) from the Italian coast of the Mediterranean Sea and in livers of ringed seals (Phoca hispida), gray seals (Halichoerus grypus), white-tailed sea eagles (Haliaeetus albicilla), and Atlantic salmon (Salmo salar) from coastal areas of the Baltic Sea. PFOS was detected in all of the wildlife species analyzed. Concentrations of PFOS in blood decreased in order of bottlenose dolphins > bluefin tuna > swordfish. Mean PFOS concentrations (61 ng/ g, wet wt) in cormorant livers collected from Sardinia Island in the Mediterranean Sea were less than the concentrations of PFOA (95 ng/g, wetwt). PFOS concentrations in cormorant livers were significantly correlated with those of PFOA. FOSA was found in 14 of 19 livers or blood samples of marine mammals from the Mediterranean Sea. The highest concentration of 878 ng FOSA/g, wet wt, was found in the liver of a common dolphin. Livers of ringed and gray seals from the Bothnian Bay in the Baltic Sea contained PFOS concentrations ranging from 130 to 1,100 ng/g, wet wt. No relationships between PFOS concentrations and ages of ringed or gray seals were observed. Concentrations of PFOS in livers of seals were 5.5-fold greater than those in corresponding blood. A significant positive correlation existed between the PFOS concentrations in liver and blood, which indicates that blood can be used for nonlethal monitoring of PFOS. Trend analysis of PFOS concentrations in livers of white-tailed sea eagles collected from eastern Germany and Poland since 1979 indicated an increase in concentrations during the 1990s. Livers of Atlantic salmons did not contain quantifiable concentrations of any of the fluorochemicals monitored. PFOS is a widespread contaminant in wildlife from the Baltic and the Mediterranean Seas, while FOSA and PFOA were detected only in certain locations indicating their sporadic spatial distribution.     

Bioaccumulation, temporal trend, and geographical distribution of synthetic musks in the marine environment

Bioaccumulation of synthetic musks in a marine food chain was investigated by analyzing marine organisms at various trophic levels, including lugworm, clam, crustacean, fish, marine mammal, and bird samples collected from tidal flat and shallow water areas of the Ariake Sea, Japan. Two of the polycyclic musks, HHCB and AHTN, were the dominant compounds found in most of the samples analyzed, whereas nitro musks were not detected in any of the organisms, suggesting greater usage of polycyclic musks relative to the nitro musks in Japan. The highest concentrations of HHCB were detected in clams (258-2730 ng/g lipid wt.), whereas HHCB concentrations in mallard and black-headed gull were low, and comparable with concentrations in fish and crab. These results are in contrast to the bioaccumulation pattern of polychlorinated biphenyls; for which a positive correlation between the concentration and the trophic status of organisms was found. Such a difference in the bioaccumulation is probably due to the metabolism and elimination of HHCB in higher trophic organisms. Temporal trends in concentrations of synthetic musks were examined by analyzing tissues of marine mammals from Japanese coastal waters collected during 1977-2005. HHCB concentrations in marine mammals have shown significant increase since the early 1990s, suggesting a continuous input of this compound into the marine environment. Comparison of the time trend for HHCB with those for PCBs and PBDEs suggested that the rates of increase in HHCB concentrations were higher than the other classes of pollutants. To examine the geographical distribution of HHCB, we have analyzed tissues of fish, marine mammals, and birds collected from several locations. Synthetic musks were not detected in a sperm whale (pelagic species) from Japanese coastal water and in eggs of south polar skua from Antarctica. While the number of samples analyzed is limited, these results imply a lack of long-range transportation potential of synthetic musks in the environment.     

Levels of polybrominated diphenyl ether (PBDE) flame retardants in animals representing different trophic levels of the North Sea food Web

The levels of individual PBDE congeners were investigated in the invertebrate species whelk (Buccinum undatum), seastar (Asterias rubens), and hermit crab (Pagurus bernhardus), the gadoid fish species whiting (Merlangius merlangus) and cod (Gadus morhua), and the marine mammal species harbor seal (Phoca vitulina) and harbor porpoise (Phocoena phocoena). These species are all important representatives of different trophic levels of the North Sea food web. All six major PBDE congeners detected (BDEs 28, 47, 99, 100, 153, and 154) are most prevalent in the commercial Penta-BDE formulation. There is no evidence for the occurrence of the Octa-BDE formulation in the North Sea food web, since its dominant congener, BDE183, was never detected. BDE209, the main congener (> 97%) in the Deca-BDE formulation, was detected only in a minority of the samples and always in concentrations around the limit of detection. Since BDE209 is often the major BDE congener in sediments from the area, the main reason for its low concentrations in biota from the North Sea seems to be a relatively low bioaccumulation potential. This can either be due to a low uptake rate of the very large molecule or a relatively rapid excretion after biotransformation. Since all invertebrates investigated are sentinel species, they are highly representative for the area of capture. The highest lipid-normalized concentrations of PBDEs in the invertebrates occurred near the mouth of the river Tees at the East coast of the UK. The geographical distribution of the PBDEs can be explained by the residual currents in the area. The direction of these currents differs between the summer and the winter season as a result of the presence or absence of vertical summer stratification of the deeper waters north of the Dogger Bank. Summer stratification results in the development of a density-driven bottom water current formed after the onset of vertical stratification of the water column in May leaving the UK coast near Flamborough Head toward the Dogger Bank. In winter, the residual currents run in a more southerly direction and follow the UK coastline. The distribution pattern of the PCBs and p,p'-DDE in the invertebrates was entirely different from that of the PBDEs, which could be expected, since the use of these organochlorines in western Europe peaked in the 1960s and 1970s but has been forbidden more than two decades ago, whereas the production and use of the penta-BDE formulation is of a more recent origin. The higher trophic levels of the North Sea food web were represented by the predatory gadoid fish species whiting and cod and the marine mammal species harbor seal and harbor porpoise. The lipid-normalized levels of the six major PBDE congeners in fish were similar to the levels in the invertebrates, but a biomagnification step in concentrations of generally more than an order of magnitude occurred from gadoid fish to marine mammals. Based on the limited number of samples, no differences could be observed between harbor seal and harbor porpoise. In summary, the results in three species of sentinel invertebrates from a network of stations covering a major part of the North Sea basin showed that the estuary of the river Tees at the UK East coast is a major source for tri- to hexa-PBDEs. Throughout the food-chain, the most marked increase in (lipid-normalized) levels of all six PBDE congeners occurred from predatory (gadoid) fish to marine mammals, agreeing with the transition from gill-breathing to lung-breathing animals. This has serious consequences for the route of elimination of POPs, since their elimination from the blood into the ambient seawater via the gill-membrane is no longer possible.     

Thiols in coastal waters of the western North Sea and English Channel

Thiols were determined in coastal waters of the western North Sea and English Channel. Detection was carried out on-board ship on-line by flow-analysis with detection by cathodic stripping voltammetry and calibration with thiourea. The thiol concentrations ranged from 0.70 to 3.60 nM (thiourea equivalents) and were found to vary over a relatively short distance perpendicular to the coast. Low concentrations in the area of greatest estuarine input (the Humber-Wash area) indicated that the thiols did not originate from low-salinity waters. Instead, variations in the thiol concentration were found to parallel those of chlorophyll. This correlation was confirmed by depth profiles which showed a trend for the thiols similar to that of chlorophyll. The data demonstrates that thiols are more widespread than anticipated, and that marine phytoplankton is an important source of the thiols. In view of their known ability to bind with metals, these data indicate that the thiols could be an important candidate to act as such ligands in the marine system. The measurements gave no evidence for the presence of sulfide in these waters which means that it must be present at less than 20% of the detected thiol levels.     

Occurrence of perfluorooctane sulfonate and other perfluorinated alkylated substances in harbor porpoises from the Black Sea

Perfluorooctane sulfonate (PFOS) and other perfluorinated alkylated substances (PFAS) were determined in liver, kidney, muscle, brain, and blubber samples of 31 harbor porpoises (Phocoena phocoena relicta) of different age and sex stranded along the Ukrainian coast of the Black Sea. In all individuals and in all tissues, PFOS was the predominant PFAS, accounting for on average 90% of the measured PFAS load. PFOS concentrations were the highest in liver (327+/-351 ng/g wet wt) and kidney (147 +/-262 ng/g wet wt) tissue, and lower in blubber (18+/-8 ng/g wet wt), muscle (41+/-50 ng/g wet wt), and brain (24 +/-23 ng/g wetwt). No significant differences could be determined between males and females, nor between juvenile and adult animals (p > 0.05). Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid could be detected in liver tissue of approximately 25% of the individuals. Perfluorobutane sulfonate, perfluorobutanoic acid, and perfluorooctanoic acid were not detected in any of the porpoise livers. Although we investigated a potential intraspecies segregation according to the source of prey, using stable isotopes, no statistically significant correlation between PFOS concentrations and stable isotopes could be determined. It is, however, noteworthy that the contamination by PFOS in the Black Sea harbor porpoises is comparable to levels found in porpoises from the German Baltic Sea and from coastal areas near Denmark and, therefore, might pose a threat to this population.     

Perfluorinated chemicals infiltrate ocean waters: link between exposure levels and stable isotope ratios in marine mammals

This is the first study to report on concentrations of perfluorinated organochemicals (FOCs) in marine mammals stranded along the southern North Sea coast in relation to stable nitrogen and carbon isotope ratios (delta15N and delta13C). The presence of FOCs in top predators such as marine mammals would indicate a potential biomagnification of these compounds and their widespread occurrence. Liver and kidney tissues of nine marine mammal species have been sampled. Among all the measured FOCs compounds, PFOS (perfluorooctane sulfonate) was predominant in terms of concentration. The highest PFOS concentrations were found in the liver of harbor seal compared to white-beaked dolphin, harbor porpoise, gray seal, sperm whale, white-sided dolphin, striped dolphin, fin whale, and hooded seal. PFOS concentrations differed significantly between sexes and age classes in harbor porpoises. Stable isotope measurements (delta13C and delta15N) were used in this study to describe the behavior of contaminants in food webs. We found a significant (p < 0.05) linear relationship between PFOS concentrations in livers of harbor porpoises and both muscle delta13C and delta15N measurements. Harbor and gray seals and white-beaked dolphin, which displayed the highest trophic position, contained the highest PFOS levels, while offshore feeders such as sperm whales, fin whales, striped dolphin, and white-sided dolphin showed lower PFOS concentrations than inshore species.     

Retrospective monitoring of alkylphenols and alkylphenol monoethoxylates in aquatic biota from 1985 to 2001: results from the German Environmental Specimen Bank

Breams (Abramis brama) and zebra mussels (Dreissena polymorpha) from freshwater, and common mussels (Mytilus edulis) from marine ecosystems, archived in the German Environmental Specimen Bankwere analyzed for the presence of 4-nonylphenol (NP), 4-tert-octylphenol (OP), nonylphenol monoethoxylate (NP1EO), and octylphenol monoethoxylate (OP1EO). The samples were collected in the German rivers Elbe, Rhine, and Saar, and in Lake Belau between 1992 and 2001, as well as in the North Sea and Baltic Sea between 1985 and 2001. The main purpose of the study was to investigate the effectiveness of imposed reduction measures regarding the use of alkylphenol ethoxylates. NP1EO and OP were detected in all breams. NP was predominantly above the limit of quantification (LOQ, 2 ng/g; all data on a wet weight basis), and OP1EO was mostly below the LOQ (0.2 ng/g). Maximal concentrations of 112 ng/g NP, 259 ng/g NP1EO, 5.5 ng/g OP, and 2.6 ng/g OP1EO were found in Saar breams from 1994. NP was detected in all zebra mussels from the river Elbe (up to 41 ng/g), whereas in rather few samples OP and NP1EO were found at low levels. OP1EO was not detected in any sample. Concentrations in mussels and breams from the reference site Lake Belau were below the LOQ for all compounds. In marine biota NP was found until 1997 with maximum concentrations up to 9.7 ng/g, whereas NP1EO was detected at levels between 1.7 and 12.9 ng/g in very few samples collected at the end of the 1980s. A tendency of the concentrations to decrease was obvious for all sampling sites; it was most pronounced for NP1EO and NP after 1996/1997. The effectiveness of the reduction measures is most evident at the Saar sampling site Güdingen and the North Sea sampling site Eckwarderh?rne.     

Retrospective monitoring of organotin compounds in marine biota from 1985 to 1999: results from the German Environmental Specimen Bank

In archived samples from the German Environmental Specimen Bank, organotin compounds including tributyltin (TBT) and triphenyltin (TPT) as well as their degradation products were quantified. Biota samples from North Sea and Baltic Sea areas were analyzed by gas chromatography/atomic emission detection-coupling after extraction and Grignard or ethylborate derivatization. TBT and TPT were detected in nearly all samples. A decrease of TPT contamination was observed in bladder wrack, common mussels, and eelpout muscle tissues in the period 1985-1999. In this period, TPT concentrations in North Sea mussels decreased from 98 to 7 ng/g (as organotin cation concentration in wet tissue). Concentrations of TBT remained relatively constant with 17 +/- 3 ng/g for mussels from a site with nearby marine traffic and 8 +/- 2 ng/g for a more remote area. The results reflect that TBT is still used as a biocide in antifouling paints whereas the use of TPT as a co-toxicant in such preparations had been ceased in the 1980s. The fact that the use of TBT in antifouling paints was banned in 1991 for small boats within the European Community seems not to have resulted in a decrease of TBT levels in marine biota.     

Characteristics of dissolved organic matter in Baltic coastal sea ice: allochthonous or autochthonous origins?

The origin of dissolved organic matter (DOM) within sea ice in coastal waters of the Baltic Sea was investigated using parallel factor (PARAFAC) analysis of DOM fluorescence. Sea ice DOM had distinctly different fluorescence characteristics than that of the underlying humic-rich waters and was dominated by protein-like fluorescence signals. PARAFAC analysis identified five fluorescent components, all of which were present in both sea ice and water. Three humic components were negatively correlated to salinity and concluded to be terrestrially derived material. Baltic Sea ice DOM was found to be a mixture of humic material from the underlying water column incorporated during ice formation and autochthonous material produced by organisms within the ice. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations were correlated to the humic fluorescence, indicating that the majority of the organic carbon and nitrogen in Baltic Sea ice is bound in terrestrial humic material trapped within the ice. This has implications for our understanding of sea ice carbon cycling in regions influenced by riverine input (e.g., Baltic and Arctic coastal waters), as the susceptibility of DOM to degradation and remineralization is largely determined by its source.     

Aluminium content in edible parts of seafood

Samples of the edible parts of different fish species and of crustacean and molluscan shellfish were collected in the North Sea, the Barents Sea, the Baltic Sea, the Northeast Atlantic, and in Greenland waters. Most of the aluminium concentrations in fillets of lean and fatty fish were lower than 0.2?mg Al/kg wet weight. Exceptions were the aluminium concentrations in fillets of fish caught near an aluminium smelting plant (up to 1?mg Al/kg wet weight). Presumably a connection between the aluminium content in sea water and the fish fillets is responsible for this. The investigations of fillets of saithe, haddock, and cod with different lengths (age) showed that the aluminium levels decreased with increasing length, however, the decrease was not significant. An aluminium accumulation in muscle tissue with increasing age could not be detected. A comparison between fillets and different organs of cod showed higher aluminium concentrations in organs, especially in gills. The aluminium intake via gills, which are in continuous contact with the ambient water, is responsible for this. In the edible part of crustacean and molluscan shellfish higher aluminium concentrations (up to 5?mg Al/kg wet weight) were detected. The different feed spectrum and metabolism of these species seem to be responsible for the higher aluminium accumulation in marine crustacean and molluscan shellfish.     

Polybrominated diphenyl ethers and organochlorines in archived northern fur seal samples from the Pacific coast of Japan, 1972-1998

The present study clearly indicated possible prolonged and chronic marine pollution by polybrominated diphenyl ethers (PBDEs) unless the international regulatory measures are reinforced substantially. Fat tissues of female northern fur seals (Callorhinus ursinus), collected at 10 time periods between 1972 and 1998 from the Pacific coast of northern Japan, were analyzed for PBDEs and organochlorine compounds (OCs). PCBs and DDTs were the predominant contaminants in the fur seal samples. PBDEs were detected in all the samples analyzed, the values ranging from 0.33 to 100 ng/g lipid wt. with predominance of BDE-47. The lowest PBDE levels were in the fur seals collected in 1972, with the peak concentration around 1991-1994 and then decreased to about 50% in 1997-1998. Compositions of higher brominated congeners increased since 1972, while some lower brominated congeners decreased, implying a change in the pattern of use, particularly the increased use of highly brominated diphenyl ethers during 1972-1998. In the meantime, PCB compositions in fur seals showed no temporal variation, suggesting a continuous input of PCBs into the marine environment in significant quantities. As peak concentrations of PBDEs occurred later than OCs, it is essential to follow up the patterns of PBDEs pollution that may be of great concern in the future. To our knowledge, this is the first report on the contamination by PBDEs in marine mammals from the Asia-Pacific waters.     

Time trends and transplacental transfer of perfluorinated compounds in melon-headed whales stranded along the Japanese coast in 1982, 2001/2002, and 2006

As a result of the phase-out of production of perfluorooctanesulfonyl-based compounds by a major producer, concentrations of perfluorooctanesulfonate (PFOS) in marine mammals from North American and European coastal waters have been declining since the early 2000s. Nevertheless, temporal trends in perfluorochemical (PFC) concentrations in marine mammals from Asian coastal waters have not been examined. In this study, PFCs were determined in livers of melon-headed whales (Peponocephala electra) collected along the coast of Japan, from three mass strandings that occurred during the past 25 years. Concentrations of nine PFCs were determined in livers of 48 melon-headed whales that were collected during strandings in 1982, 2001/2002, and 2006. In addition, concentrations in liver tissues obtained from two pregnant females and their fetuses were compared for determination of transplacental transfer rates of PFCs during gestation. PFOS and perfluorooctanesulfonamide (PFOSA) were the predominant PFCs found in livers of melon-headed whales collected in 1982 (n = 22). PFOS, PFOSA, perfluoroundecanoate (PFUnDA), perfluorododecanoate (PFDoDA), perfluorodecanoate (PFDA), and perfluorononanoate (PFNA) were found in whales collected in 2001/2002 (n = 21) and in 2006 (n = 5). Concentrations of PFOS and PFOSA were approximately 10-fold higher in 2001/2002 than in 1982. Whereas concentrations of PFOSA then declined by 2-fold from 2001/ 2002 to 2006, concentrations of PFOS and perfluorocarboxylates did not decline after 2001/2002. Conversely, concentrations of PFNA and PFDA increased significantly from 2001/2002 to 2006. The proportion of perfluoroalkylsulfonates in total PFC concentrations decreased from 75% in 1982 to 51% in 2006. Conversely, the contribution of perfluorocarboxylates to total PFC concentrations increased from 25% in 1982 to 49% in 2006. PFUnDA was the major perfluorocarboxylate found in whale livers collected after 2000. Analysis of paired samples of mother-fetus demonstrated that the transplacental transfer rates of PFCs were higher than those for PCBs and PBDEs.     

Is fish a major source of fluorinated surfactants and repellents in humans living on the Baltic Coast?

Concentrations of 19 perfluorochemicals have been quantified in human blood and in some marine food resources from the region of the Gulf of Gda?sk at the Baltic Sea south coast in Poland. We indicate that in addition to PFOS and PFOA, a further 8 perfluorochemicals bioaccumulate in the human body. Food chain is an important route of exposure for all 10 perfluoroalkyl compounds detected in nonoccupationally exposed humans. Individuals who declared to have a high fish intake in their diet (mainly Baltic fish) on average contained the highest load of all 10 fluorochemicals when compared with the other human subpopulations. Baltic seafood has been found to highly influence human body burden of PFHxS, PFOS, PFOSA, PFHxA, PFHpA, PFNA, PFDA, PFUnDA, and PFDoDA, and to a lesser extent PFOA.     

Global pollution monitoring of polybrominated diphenyl ethers using skipjack tuna as a bioindicator

To elucidate the global distribution of polybrominated diphenyl ethers (PBDEs), these chemicals were determined in the muscle of skipjack tuna (Katsuwonus pelamis) collected from offshore waters of various regions in the world (Japan, Taiwan, Philippines, Indonesia, Seychelles, and Brazil, and the Japan Sea, East China Sea, South China Sea, Indian Ocean, and North Pacific Ocean). PBDEs were detected in almost all the skipjack tuna collected from the locations surveyed (from < 0.1 to 53 ng/g of lipid), indicating widespread contamination by these compounds in the marine environment. Residue levels of PBDEs in these samples from the northern hemisphere seem to be higher than those from the southern hemisphere, which is plausibly due to larger usage of these compounds in the northern hemisphere. Higher concentrations of PBDEs were detected in the samples from waters around the East China Sea (up to 53 ng/g of lipid). Developing countries around the East China Sea are supposedly the "hot spots" releasing these chemicals into the marine environment. With regard to the composition of PBDE congeners, the percentage contribution by lower brominated congeners (BDE15, -28, and -47) showed an increasing trend with increasing latitude. On the other hand, higher brominated congeners (BDE153, -154, and -183) showed a reverse trend. These patterns suggest that lower brominated congeners of PBDEs (di-, tri-, and tetra-BDEs) were preferentially transported from pollution sources to northern colder regions through the atmosphere. PBDEs may have a high potency to cause global pollution like PCBs.     

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.     

Alkylphenolic compounds in edible molluscs of the Adriatic Sea (Italy)

This paper reports the first group of results on alkylphenol (APE) contamination of seafood in the Adriatic Sea, in the framework of a national project on the quality of this Sea (PRISMA 2). Nonylphenol (NP), octylphenol (OP), and their ethoxylates (NPE and OPE) were detected in edible molluscs, either filter feeders or predators (clams, mussels, cuttlefishes, and squids), caught from 15 harbors along the Italian coast in the Adriatic Sea in 1997. NP was the compound found always at levels much higher than the other APEs in all the examined species. It reached the maximum concentration of 696 ng/g fresh weight in the squids from the central Adriatic Sea. OP generally occurred at levels 30 times lower than NP. OP was found up to a level of 18.6 ng/g in squids from central Adriatic Sea. OPE was the compound always spotted at the lowest concentrations, up to 0.43 ng/g. NPE was always below the detection limit. The pattern of contamination in the three areas examined was different between bivalve and cephalopod species. No exhaustive risk assessment for marine organisms and human health can be conducted on the basis of these results because data are insufficient. Yet, the occurrence of NP suggests a negligible risk for mussels, which represent the only molluscs for which data are adequate. As to the possible human health implications, the consumption of molluscs of the Adriatic Sea implies APE intakes that are some orders of magnitude lower than those responsible for toxic effects in laboratory animals. Despite these apparently low risks for mussels and human health, the reasons for concern still remain because the levels of alkylphenols found in this study indicate a general contamination of the Adriatic Sea even far from the cost. Furthermore, these levels might represent an unacceptable hazard for other marine organisms. Finally, they contribute to the general environmental estrogen pool.     

Global distribution of perfluorooctane sulfonate in wildlife

Here we report, for the first time, on the global distribution of perfluorooctanesulfonate (PFOS), a fluorinated organic contaminant. PFOS was measured in the tissues of wildlife, including, fish, birds, and marine mammals. Some of the species studied include bald eagles, polar bears, albatrosses, and various species of seals. Samples were collected from urbanized areas in North America, especially the Great Lakes region and coastal marine areas and rivers, and Europe. Samples were also collected from a number of more remote, less urbanized locations such as the Arctic and the North Pacific Oceans. The results demonstrated that PFOS is widespread in the environment. Concentrations of PFOS in animals from relatively more populated and industrialized regions, such as the North American Great Lakes, Baltic Sea, and Mediterranean Sea,were greaterthan those in animals from remote marine locations. Fish-eating, predatory animals such as mink and bald eagles contained concentrations of PFOS that were greater than the concentrations in their diets. This suggests that PFOS can bioaccumulate to higher trophic levels of the food chain. Currently available data indicate that the concentrations of PFOS in wildlife are less than those required to cause adverse effects in laboratory animals.     

Why do organochlorine differences between arctic regions vary among trophic levels?

Statistical analysis of organochlorine contaminants (OCs) in marine mammals has shown that, for most OCs, the European Arctic is more contaminated than the Canadian and U.S. Arctic. Recently, comparison of OC concentration ranges in seabirds, arctic cod (Boregadus saida), and zooplankton, found no difference between these regions. To address these inconsistencies, marine food web OC data from the European (central Barents Sea (CBS)) and Canadian Arctic (Northwater Polynya (NOW)) were simultaneously statistically analyzed. In general, concentrations of OCs were greater in seabirds and ringed seals (Phoca hispida) from the CBS as compared to the NOW; consistent with circumpolar trends observed in marine mammals. In contrast, levels of OCs were generally similar in zooplankton and arctic cod between the CBS and NOW. The main exception is HCH which had greater levels in the NOW across all trophic levels because of the greater proximity to sources in eastern Asia. The lack of differences in OC concentrations in zooplankton and Arctic cod from the European and Canadian Arctic suggest that regional differences in OC contamination in the Arctic have evened out. Reduced regional differences were not observed in marine mammals or seabirds because they are long-lived and also acquire contaminants from maternal transfer and hence reflect levels from the past when the European Arctic was more contaminated than the Canadian Arctic. In addition, seabirds may reflect exposure from other areas. This study highlights the potential problem of comparing spatial trends by using means and confidence intervals as compared to simultaneous statistical analysis of raw data. Differences in the spatial trends of OCs between trophic levels in the Arctic are important for consideration when assessing regional differences in spatial and temporal trends of discontinued and current-use contaminants.     

Evaluating a model of the historical behavior of two hexachlorocyclohexanes in the Baltic Sea environment

The POPCYCLING-Baltic model, a non-steady-state multicompartmental mass balance model of long-term chemical fate in the Baltic Sea environment, is evaluated for its capability to simulate the behavior of alpha- and gamma-hexachlorocyclohexane isomers from 1970 to 2000. The model predicts HCH concentrations in air, seawater, marine sediments, and needles well within an order of magnitude, often within a factor of 2, and reproduces major features of the observed differences in space and time. The spatial and temporal patterns of HCHs in the Baltic Sea environment are found to be controlled mostly by chemical input, both through direct emissions within the drainage basin and through advective inflow from adjacent areas, but variable environmental conditions can significantly modify the spatial distribution patterns. Simulations with different boundary conditions, i.e., variable assumptions concerning advective atmospheric inflow, suggest that sources within the drainage basin alone are not capable of explaining the observed HCH levels and that significant transport into the region must occur. Deviations between predicted and measured HCH concentrations can often be explained by uncertain estimates of usage and advective import, illustrating the usefulness of the model for evaluating the reasonability of emission estimates and boundary conditions.