Tissue distribution of perfluorinated surfactants in common guillemot (Uria aalge) from the Baltic Sea

Perfluorinated alkyl surfactants (PFAS) were investigated in tissues and organs of the common guillemot (Uria aalge) from the Baltic Sea. Concentrations of 11 perfluorinated carboxylates, four perfluorinated sulfonates, and perfluorooctane sulfonamide were determined in egg, liver, kidney, and muscle of adult guillemot, as well as in liver from chicks, all sampled in 1989. Additionally, whole herring homogenates from 2005 were analyzed, herring comprising a large part of guillemot's diet. Quantifiable concentrations of PFAS were found in all samples. Perfluorooctane sulfonate (PFOS) was predominant, followed by perfluorotridecanoate (PFTriDA) and perfluoroundecanoate (PFUnDA). The median concentration of PFOS was highest in eggs (325 ng/g wet weight (w wt)) followed by chick liver (309 ng/g w wt), kidney (127 ng/g w wt), adult liver (121 ng/g w wt), and muscle (14 ng/g w wt). Comparatively low levels of PFOS were found in herring, leaving a blurred picture of uptake routes. PFAS concentrations in livers of male and female guillemots did not differ significantly. Some PFAS showed higher concentrations in eggs than in female livers. The ratio of levels in egg/female liver, indicating mother-to-egg transfer capacity, increased with increasing PFAS chain length. PFOS showed a higher tendency for transfer than carboxylates of carbon chain lengths C9-C13.     

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.     

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus)

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.     

Polybrominated diphenyl ethers, perfluorinated compounds and chlorinated pesticides in swordfish (Xiphias gladius) from the Mediterranean Sea

The relative isolation of the Mediterranean population, their feeding habits, and the widespread use of their fillets for human consumption make the Mediterranean swordfish, Xiphias gladius, an interesting species from an ecotoxicological and commercial point of views. High resolution gas chromatography and tandem mass spectrometry detected 19 PBDE congeners, perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA), hexachlorobenzene (HCB), p,p' and o,p' isomers of DDT, DDE, and DDD in all samples. The presence of PBDEs was reported for the first time in Mediterranean swordfish from the South Tyrrhenian Sea; total PBDE concentrations were 2218 +/- 3291 and 612 +/- 598 pg/g wet wt in the liver and in the muscle, respectively. Significant correlations were identified between BDE47 and sigmaPBDE liver concentrations versus sex and sexual maturity of specimens. The lipid-normalized concentrations ratio BDEn(liver)/BDEn(muscle+liver) suggested that this species mostly accumulates POPs in the liver. PFOS and PFOA were below the LOD (1.5 and 3 ng/g wet wt, respectively) in all the samples. The sigmaDDTs was 155 +/- 125 and 309 +/- 273 ng/g wet wt in the muscle and the liver, respectively. The estimated daily ingestion of PBDEs and DDTs through diet was lower than the acceptable weekly intakes proposed by the World Health Organization.     

Perfluorinated alkyl substances in plasma, liver, brain, and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian arctic

Recent environmental surveys have ascertained the widespread occurrence of perfluorinated alkyl substances (PFAS) in tissues of wildlife from the Arctic. In the present study, we investigated the distribution of a suite of PFAS in plasma, liver, brain, and egg samples from adult glaucous gulls (Larus hyperboreus), an apex scavenger-predator seabird breeding in the Norwegian Arctic. Perfluorooctane sulfonate (PFOS) was the predominant PFAS in all samples and was present at concentrations that are the highest reported thus far in any arctic seabird species and populations. Among the body compartment/ tissue samples analyzed, PFOS was highest in plasma (48.1-349 ng/g wet weight (ww)), followed by liver approximately equal to egg > brain. Perfluorocarboxylic acids (PFCAs) with 8-15 carbon (C) atoms were found, with the highest concentrations determined in plasma (sum PFCA: 41.8-262 ng/g ww), whereas 5C- and 6C-PFCAs were below the limits of detection. Perfluorobutane sulfonate, perfluorooctane sulfonamide, and four saturated (8:2 FTCA and 10:2 FTCA) and unsaturated (8:2 FTUCA and 10:2 FTUCA) fluorotelomer carboxylic acids were not detected in any samples. Perfluorohexane sulfonate was measured at concentrations up to 2.71 ng/g ww. The accumulation profiles of PFCAs were characterized by high proportions of the long and odd-numbered carbon-chain-length compounds, namely perfluoroundecanoic (11C) and perfluorotridecanoic acid (13C), although their individual contribution differed between the matrixes analyzed. Current PFAS concentrations suggest a bioaccumulation potential in Norwegian arctic glaucous gulls that needs to be assessed as part of a broad organohalogen contaminant cocktail with potential for mediating biological processes in this vulnerable top-predator marine species.     

Fluorinated organic compounds in an eastern Arctic marine food web

An eastern Arctic marine food web was analyzed for perfluorooctanesulfonate (PFOS, C8F17SO3-), perfluorooctanoate (PFOA, C7F15COO-), perfluorooctane sulfonamide (PFOSA, C8F17SO2NH2), and N-ethylperfluorooctane sulfonamide (N-EtPFOSA, C8F17SO2NHCH2CH3) to examine the extent of bioaccumulation. PFOS was detected in all species analyzed, and mean concentrations ranged from 0.28 +/- 0.09 ng/g (arithmetic mean +/- 1 standard error, wet wt, whole body) in clams (Mya truncata) to 20.2 +/- 3.9 ng/g (wet wt, liver) in glaucous gulls (Larus hyperboreus). PFOA was detected in approximately 40% of the samples analyzed at concentrations generally smaller than those found for PFOS; the greatest concentrations were observed in zooplankton (2.6 +/- 0.3 ng/g, wet wt). N-EtPFOSA was detected in all species except redfish with mean concentrations ranging from 0.39 +/- 0.07 ng/g (wet wt) in mixed zooplankton to 92.8 +/- 41.9 ng/g (wet wt) in Arctic cod (Boreogadus saida). This is the first report of N-EtPFOSA in Arctic biota. PFOSA was only detected in livers of beluga (Delphinapterus leucas) (20.9 +/- 7.9 ng/g, wet wt) and narwhal (Monodon monoceros) (6.2 +/- 2.3 ng/g, wet wt), suggesting that N-EtPFOSA and other PFOSA-type precursors are likely present but are being biotransformed to PFOSA. A positive linear relationship was found between PFOS concentrations (wet wt) and trophic level (TL), based on delta15N values, (r2 = 0.51, p < 0.0001) resulting in a trophic magnification factor of 3.1. TL-corrected biomagnification factor estimates for PFOS ranged from 0.4 to 9. Both results indicate that PFOS biomagnifies in the Arctic marine food web when liver concentrations of PFOS are used for seabirds and marine mammals. However, transformation of N-EtPFOSA and PFOSA and potential other perfluorinated compounds to PFOS may contribute to PFOS levels in marine mammals and may inflate estimated biomagnification values. None of the other fluorinated compounds (N-EtPFOSA, PFOSA, and PFOA) were found to have a significant relationship with TL, but BMF(TL) values of these compounds were often >1, suggesting potential for these compounds to biomagnify. The presence of perfluorinated compounds in seabirds and mammals provides evidence that trophic transfer is an important exposure route of these chemicals to Arctic biota.     

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.     

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.     

江西省畜禽产品中全氟辛酸和全氟辛烷磺酸污染情况调查与分析

为了探索江西省畜禽产品中全氟辛酸（perfluorooctanoic acid,PFOA）和全氟辛烷磺酸（perfluorooctanesulfonate,PFOS）的污染现状,采用超高效液相色谱-三重四极杆串联质谱对江西省5 个畜禽主产市市售猪、鸡、鸭各组织（n=260）样品中PFOS和PFOA的污染水平进行了分析。结果表明：以湿质量计算可知,鸡血中PFOA的污染水平最高,为0.52 ng/g,其次为猪肝（0.24 ng/g）,然后依次为鸡肝（0.14 ng/g）、鸭血（0.12 ng/g）、鸭肝（0.029 ng/g）,猪肉、鸡肉、鸭肉和猪血中均未检出PFOA的污染;PFOS仅在猪肝中检出,其均值为0.20 ng/g。对人体健康风险评价结果显示,江西省猪、鸡和鸭各组织中PFOA和PFOS不会对人体健康造成即时危害。     

Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses

Perfluorooctane sulfonate (PFOS) was measured in 161 samples of liver, kidney, blood, or egg yolk from 21 species of fish-eating water birds collected in the United States including albatrosses from Sand Island, Midway Atoll, in the central North Pacific Ocean. Concentrations of PFOS in the blood plasma of bald eagles collected fromthe midwestern United States ranged from 13 to 2,220 ng/mL (mean: 330 ng/mL), except one sample that did not contain quantifiable concentrations of PFOS. Concentrations of PFOS were greater in blood plasma than in whole blood. Among 82 livers from various species of birds from inland or coastal U.S. locations, Brandt's cormorant from San Diego, CA, contained the greatest concentration of PFOS (1,780 ng/g, wet wt). PFOS was also found in the sera of albatrosses from the central North Pacific Ocean at concentrations ranging from 3 to 34 ng/mL. Occurrence of PFOS in birds from remote marine locations suggests widespread distribution of PFOS and related fluorochemicals in the environment.     

Perfluorooctanesulfonate and related fluorochemicals in albatrosses, elephant seals, penguins, and polar skuas from the Southern Ocean

Perfluorinated chemicals (PFCs) have been used as surfactants in industrial and commercial products for over 50 years. Earlier studies of the geographical distribution of PFCs focused primarily on the Northern Hemisphere, while little attention was paid to the Southern Hemisphere. In this study, livers from eight species of albatrosses, blood from elephant seal, and blood and eggs from penguins and polar skua collected from the Southern Ocean and the Antarctic during 1995-2005 were analyzed for 10 PFCs. In addition, for comparison with the Southern Ocean samples, we analyzed liver, sera, and eggs from two species of albatrosses from Midway Atoll in the North Pacific Ocean. Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were found in livers of albatrosses from the Southern Ocean. PFOS was the major contaminant, although the concentrations were <5 ng/g, wet wt, in 92% of the albatross livers analyzed. PFOA was detected in 30% of the albatross livers, with a concentration range of <0.6-2.45 ng/g,wet wt. Other PFCs, including long-chain perfluorocarboxylates (PFCAs), were below the limits of quantitation in livers of albatrosses from the Southern Ocean. In liver, sera, and eggs of albatrosses from the North Pacific Ocean, long-chain PFCAs (perfluorononanoate, perfluorodecanoate, perfluoroundecanoate, and perfluorododecanoate) were found at concentrations similar to those of PFOS and PFOA. The mean concentration of PFOS in livers of Laysan albatrosses from the North Pacific Ocean (5.1 ng/g, wet wt) was higher than that in several species of albatrosses from the Southern Ocean (2.2 ng/g, wetwt). Species-specific differences in the concentrations of PFOS were noted among Southern Ocean albatrosses, whereas geographical differences in PFOS concentrations among the Indian Ocean, South Pacific Ocean, and South Atlantic Ocean were insignificant. Concentrations of PFOS and PFOA were, respectively, 2- and 17-fold higher in liver than in sera of Laysan albatrosses. PFOS was found in the blood of elephant seals from Antarctica at concentrations ranging from <0.08 to 3.52 ng/mL. PFOS was found in eggs (2.1-3.1 ng/g) and blood (<0.24-1.4 ng/ mL) of polar skuas but was not detected in penguins from Antarctica. Our study documents the existence of low but detectable levels of PFOS and PFOA in Southern Hemisphere fauna, suggesting distribution of these compounds on a global scale.     

Trends of perfluorinated alkyl substances in herring gull eggs from two coastal colonies in northern Norway: 1983-2003

The present study reports on concentrations, patterns, and temporal trends (1983, 1993, and 2003) of 16 perfluorinated alkyl substances (PFAS) in whole eggs of herring gulls (Larus argentatus) from two geographically isolated colonies in northern Norway. Perfluorooctane sulfonate (PFOS) was the predominant PFAS in all eggs with mean concentrations up to 42 ng/g wet weight (ww) in samples from 2003. Perfluorohexane sulfonate (PFHxS) and perfluorodecane sulfonate (PFDcS) were found at concentrations several orders of magnitude lower than PFOS. The general accumulation profile of perfluorocarboxylates (PFCAs) in herring gull eggs was characterized by high proportions of odd and long carbon (C) chain length compounds in which perfluoroundecanoate (C11) and perfluorotridecanoate (C13) dominated with mean concentrations up to 4.2 and 2.8 ng/g ww, respectively. In both colonies PFOS concentrations in eggs showed a nearly 2-fold significant increase from 1983 to 1993, followed by a leveling off up to 2003. A comparable trend was found for PFHxS, whereas PFDcS was found to increase also between 1993 and 2003. PFCA concentrations showed marked significant increases during 1983-1993 associated with either a weak rise post-1993 (C8- to C11-PFCAs), although nonsignificant, or leveling off (C12- and C13-PFCAs). However, the composition of individual PFCAs (C8 to C15) to the summed concentrations of those eight PFCAs highly differed between the colonies and sampling years investigated. Present results suggest that direct and indirect local- and/or remote-sourced inputs (atmospheric and waterborne) of PFCAs have changed over the last two decades in these two coastal areas of Northern Norway.     

Occurrence of synthetic musk fragrances in marine mammals and sharks from Japanese coastal waters

In this study, the occurrence of the polycyclic musk fragrances HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyltetrahydeonaphthalene) in marine mammals and sharks collected from Japanese coastal waters is reported. HHCB was present in the blubbers of all finless porpoises (Neophocaena phocaenoides) analyzed (n = 8), at levels ranging from 13 to 149 ng/g on a wet weight basis. A fetus sample of finless porpoise contained a notable concentration of HHCB (26 ng/g wet wt), suggesting transplacental transfer of this compound. Among 12 tissues and organs of a finless porpoise analyzed, the highest HHCB concentration was found in blubber, followed by kidney. This indicates that HHCB accumulates in lipid-rich tissues in marine mammals, which is similar to the accumulation profiles of persistent organochlorines, such as PCBs and DDTs. In general, the residue levels of AHTN and nitro musks were low or below the detection limits in finless porpoises, implying either less usage in Japan or high metabolic capacity of these compounds in this animal. HHCB was also found in the livers of five hammerhead sharks (Sphrna lewini) from Japanese coastal waters, at concentrations ranging from 16 to 48 ng/g wet wt. Occurrence of HHCB in higher trophic organisms strongly suggests that it is less degradable in the environment and accumulates in the top predators of marine food chains. This is the first report on the accumulation of synthetic musk fragrances in marine mammals and sharks.     

Biomagnification of perfluorinated compounds in a remote terrestrial food chain: Lichen-Caribou-wolf

The biomagnification behavior of perfluorinated carboxylates (PFCAs) and perfluorinated sulfonates (PFSAs) was studied in terrestrial food webs consisting of lichen and plants, caribou, and wolves from two remote northern areas in Canada. Six PFCAs with eight to thirteen carbons and perfluorooctane sulfonate (PFOS) were regularly detected in all species. Lowest concentrations were found for vegetation (0.02-0.26 ng/g wet weight (ww) sum (Σ) PFCAs and 0.002-0.038 ng/g ww PFOS). Wolf liver showed highest concentrations (10-18 ng/g ww ΣPFCAs and 1.4-1.7 ng/g ww PFOS) followed by caribou liver (6-10 ng/g ww ΣPFCAs and 0.7-2.2 ng/g ww PFOS). Biomagnification factors were highly tissue and substance specific. Therefore, individual whole body concentrations were calculated and used for biomagnification and trophic magnification assessment. Trophic magnification factors (TMF) were highest for PFCAs with nine to eleven carbons (TMF = 2.2-2.9) as well as PFOS (TMF = 2.3-2.6) and all but perfluorooctanoate were significantly biomagnified. The relationship of PFCA and PFSA TMFs with the chain length in the terrestrial food chain was similar to previous studies for Arctic marine mammal food web, but the absolute values of TMFs were around two times lower for this study than in the marine environment. This study demonstrates that challenges remain for applying the TMF approach to studies of biomagnification of PFCAs and PFSAs, especially for terrestrial animals.     

Spatial distribution of perfluoroalkyl contaminants in lake trout from the Great Lakes

Individual whole body homogenates of 4 year old lake trout (Salvelinus namaycush) samples collected in 2001 from each of the Great Lakes were extracted using a novel fluorophilicity cleanup step and analyzed for perfluoroalkyl compounds (PFCs). Standard addition and internal standardization were used for quantification. Results were reported (+/- SE) for perfluorinated carboxylates (PFCAs), perfluorinated sulfonates (PFSAs), and unsaturated fluorotelomer carboxylates (8:2 and 10:2 FTUCA). The lowest average concentration of sigmaPFC was found in samples from Lake Superior (13+/-1 ng g(-1)), while the highest average concentration was found in samples from Lake Erie (152+/-14 ng g(-1)). Samples from Lake Ontario (60+/-5 ng g(-1)) and Lake Huron (58 +/-10 ng g(-1)) showed similar average sigmaPFC concentrations, although the perfluorinated sulfonate/carboxylate ratios were different. The major perfluoroalkyl contaminant observed was perfluorooctane sulfonate (PFOS) with the highest concentration found in samples from Lake Erie (121+/-14 ng g(-1)), followed by samples from Lake Ontario (46+/-5 ng g(-1)), Lake Huron (39 +/-10 ng g(-1)), Lake Michigan (16+/-3 ng g(-1)), and Lake Superior (5+/-1 ng g(-1)). Perfluorodecane sulfonate (PFDS) was detected in 89% of the samples, with the highest concentration in Lake Erie samples (9.8+/-1.6 ng g(-1)), and lowest concentration in samples from Lake Superior (0.7 +/- 0.1 ng g(-1)). Statistically significant correlations were observed between PFOS and PFDS concentrations, and PFOS concentration and body weight, respectively. The PFCAs were detected in all samples, with the highest total average concentration in samples from Lake Erie (19 ng g(-1)), followed by samples from Lake Huron (16 ng g(-1)), Lake Ontario (10 ng g(-1)), Lake Michigan (9 ng g(-1)) and Lake Superior (7 ng g(-1)). The compounds with significant contributions to the sigmaPFCA concentrations were PFOA and C9-C13-PFCAs. The 8:2 FTUCA was detected at concentrations ranging between 0.1 and 0.2 ng g-1, with the highest level in samples showing also elevated concentrations of PFOA (4.4 ng g(-1) for Lake Michigan vs 1.5 ng g(-1) for all other samples). The 10:2 FTUCA was detected only in 9% of all samples (nd, 45 pg g(-1)). For those PFCs where we determined lake water concentrations, the highest log BAFs were calculated for PFOS (4.1), PFDA (3.9), and PFOSA (3.8).     

Hexabromocyclododecane in white-sided dolphins: temporal trend and stereoisomer distribution in tissues

Hexabromocyclododecane (HBCD) is a brominated flame retardant used primarily in expanded polystyrene foams and other styrene resins. Samples of blubber (n = 57) and liver (n = 16) from Atlantic white-sided dolphins, Lagenorhynchus acutus, that stranded on the eastern coast of United States between 1993 and 2004 were obtained from the National Marine Mammal Tissue Bank (NMMTB). Blubber samples from most of these animals (n = 47) were previously analyzed for polybrominated diphenyl ethers (PBDE), polychlorinated biphenyls (PCB), and several toxaphene congeners. The three most abundant diastereomers in the technical HBCD mixture (alpha-HBCD, beta-HBCD, and gamma-HBCD) and their enantiomers were determined using liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS). alpha-HBCD was found in all blubber and liver samples while beta-HBCD and gamma-HBCD were not detected in any samples. The alpha-HBCD concentration in blubber and liver ranged from 14 ng/g wet mass (19 ng/g lipid) to 280 ng/g wet mass (380 ng/g lipid) and 0.051 ng/g wet mass (2.9 ng/g lipid) to 3.6 ng/g wet mass (140 ng/g lipid), respectively. Concentrations of alpha-HBCD were 2 to 3 orders of magnitude lower than previously reported PBDE, PCB, and toxaphene concentrations in these same animals. There was not a significant temporal trend for these compounds in white-sided dolphin blubber. The enantiomeric fractions (EF) measured in blubber and liver were not statistically different and ranged from 0.34 to 0.53. Blubber EFs were significantly correlated with both alpha-HBCD concentrations and white-sided dolphin body length. In general, concentrations of HBCDs were lower in these white-sided dolphins than in cetaceans from Western Europe.     

Perfluorooctanesulfonate and related fluorinated hydrocarbons in mink and river otters from the United States

Mink and otters are good integrators of their aquatic environments and useful sentinel species for determining exposure to environmental contaminants. In this study, perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were measured in livers of mink and river otters collected from various locations in the United States. PFOS was found in all mink livers analyzed. Frequencies of occurrence of FOSA, PFHxS, and PFOA were less. The greatest concentration of PFOS measured in liver of mink was 5140 ng/g, wet weight. Maximum concentrations of FOSA, PFHxS, and PFOA in mink livers were 590, 39, and 27 ng/g, wet weight, respectively. There were no significant positive relationships between concentrations of PFOS and PFHxS or PFOA in mink livers. Concentrations of PFOS were positively correlated with those of FOSA in mink livers from Illinois. There was no significant correlation between concentrations of PFOS and lipid content in mink livers. There were no age- or sex-related differences in the concentrations of fluorochemicals in mink livers. Greater concentrations are associated with those individuals collected near urbanized and/or industrialized areas. PFOS was detected in livers of all river otters collected from Washington and Oregon at concentrations ranging from 25 to 994 ng/g, wet wt.     

Persistent perfluorinated acids in seafood collected from two cities of China

As an initial survey of human exposure to perfluorinated acids through food consumption in China, seven types of seafood collected from fish markets in two coastal cities were analyzed. Nine perfluorinated compounds were determined using HPLC coupled with ESI-MS/MS. Perfluorooctane sulfonate (PFOS) was the predominant fluorochemical and was found in all 27 seafood samples, including fish, molluscs, crabs, shrimp, oysters, mussels, and clams. Concentrations of PFOS in seafood samples ranged from 0.3 to 13.9 ng/g wet weight, with the highest concentration in mantis shrimp. The hazard ratios of noncancer risk through seafood consumption based on PFOS and perfluorooctanoic acid concentrations were calculated and were less than unity.     

Contamination and effects of perfluorochemicals in Baikal seal (Pusa sibirica). 1. Residue level, tissue distribution, and temporal trend

Concentrations of perfluorochemicals (PFCs) including perfluoroalkylsulfonates (PFSAs) and perfluoroalkylcarboxylates (PFCAs) were determined in liver and serum of Baikal seals (Pusa sibirica) collected from Lake Baikal, Russia in 2005. Among the 10 PFC compounds measured, perfluorononanoic acid (PFNA, 3.3-72 ng/g wet wt) concentrations were the highest in liver, followed by perfluorooctanesulfonate (PFOS, 2.6-38 ng/g). The accumulation profile of long-chain (C7-C12) PFCAs in particular, the predominance of PFNA, indicated that 8:2 fluorotelomer alcohol or commercially manufactured PFNA is a major local source of PFCs in Lake Baikal. No gender-related differences in the concentrations of individual PFCs or total PFCs were found. Tissues from pups and juveniles contained relatively higher concentrations of PFCs than tissues from subadults and adults, suggesting that maternal transfer of PFCs is of critical importance. Comparison of concentrations of PFCs in livers and sera collected from the same individuals of Baikal seals revealed that residue levels of PFOS, PFNA, perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) were significantly higher in liver than in serum. The concentration ratios of PFNA and PFDA between liver and serum were calculated to be 14 and 15, respectively, whereas the ratio of PFOS was 2.4. This suggests preferential retention of both PFNA and PFDA in liver. Concentrations of PFOS, PFNA, and PFDA in liver were significantly correlated with those in serum, whereas concentrations of PFUnDA were not correlated in between the two tissues, suggesting differences in pharmacokinetics among these PFCs. Temporal comparisons of hepatic PFC concentrations in seals collected between 1992 and 2005 showed that the concentrations of PFOS (p = 0.0006), PFNA (p = 0.061) and PFDA (p = 0.017) were higher in animals collected in recentyears, indicating ongoing sources of PFC contamination in Lake Baikal.