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.     

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.     

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.     

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.     

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.     

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.     

Decline in perfluorooctanesulfonate and other polyfluoroalkyl chemicals in American Red Cross adult blood donors, 2000-2006

In 2000, 3M Company, the primary global manufacturer, announced a phase-out of perfluorooctanesulfonyl fluoride (POSF, C8F17SO2F)-based materials after perfluorooctanesulfonate (PFOS, C8F17SO3-) was reported in human populations and wildlife. The purpose of this study was to determine whether PFOS and other polyfluoroalkyl concentrations in plasma samples, collected in 2006 from six American Red Cross adult blood donor centers, have declined compared to nonpaired serum samples from the same locations in 2000-2001. For each location, 100 samples were obtained evenly distributed by age (20-69 years) and sex. Analytes measured, using tandem mass spectrometry, were PFOS, perfluorooctanoate (PFOA), perfluorohexanesulfonate (PFHxS), perfluorobutanesulfonate (PFBS), N-methyl perfluorooctanesulfonamidoacetate (Me-PFOSA-AcOH), and N-ethyl perfluorooctanesulfonamidoacetate (Et-PFOSA-AcOH). The geometric mean plasma concentrations were for PFOS 14.5 ng/mL (95% CI 13.9-15.2), PFOA 3.4 ng/ mL (95% CI 3.3-3.6), and PFHxS 1.5 ng/mL (95% CI 1.4-1.6). The majority of PFBS, Me-PFOSA-AcOH, and Et-PFOSA-AcOH concentrations were less than the lower limit of quantitation. Age- and sex-adjusted geometric means were lower in 2006 (approximately 60% for PFOS, 25% for PFOA, and 30% for PFHxS) than those in 2000-2001. The declines for PFOS and PFHxS are consistent with their serum elimination half-lives and the time since the phase-out of POSF-based materials. The shorter serum elimination half-life for PFOA and its smaller percentage decline than PFOS suggests PFOA concentrations measured in the general population are unlikely to be solely attributed to POSF-based materials. Direct and indirect exposure sources of PFOA could include historic and ongoing electrochemical cell fluorination (ECF) of PFOA, telomer production of PFOA, fluorotelomer-based precursors, and other fluoropoly-mer production.     

Temporal trends of PFOS and PFOA in guillemot eggs from the Baltic Sea, 1968--2003

Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have recently been identified as ubiquitous environmental contaminants. Although they have been produced for 50 years, little is known about when they first appeared in the environment and how their concentrations have changed over time, particularly in response to the phase-out of PFOS, which began in 2000. In this study temporal trends in the concentrations of PFOS and PFOA in the Baltic Sea marine environmentwere measured using archived guillemot eggs. Samples collected from Stora Karls? (Sweden) between 1968 and 2003 were received from an environmental specimen bank and concentrations of PFOS and PFOA were analyzed using HPLC coupled to ESI-MS/MS. PFOA was not detected in any of the samples (LOD 3 ng/g), but there was an almost 30-fold increase in PFOS concentrations in the guillemot eggs during the time period, from 25 ng/g in 1968 to 614 ng/g in 2003 (wet weight). Regression analysis indicated a significant trend, increasing on average between 7 and 11% per year. A sharp peak in PFOS concentrations was observed in 1997 followed by decreasing levels up to 2002, but this cannot be linked to the PFOS phase-out, which occurred at the end of this period.     

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.     

Human donor liver and serum concentrations of perfluorooctanesulfonate and other perfluorochemicals

Perfluorooctanesulfonate (PFOS, CaF17SO3-) has been identified in the serum of nonoccupationally exposed humans and in serum and liver tissue in wildlife. The purpose of this investigation was to determine whether PFOS liver concentrations in humans are comparable to the approximate 30 ng/mL average serum concentrations reported in nonoccupationally exposed subjects. Thirty-one donors (16 male and 15 female, age range 5-74) provided serum and/or liver samples for analysis of PFOS and three other fluorochemicals: perfluorosulfonamide (PFOSA, C8F17SO2NH2), perfluorooctanoate (PFOA, C7F15CO2-), and perfluorohexanesulfonate (PFHxS, C6F13SO3-). Both sera and liver samples were extracted by ion-pair extraction and quantitatively assayed using high-performance liquid chromatography electrospray tandem mass spectrometry. Liver PFOS concentrations ranged from <4.5 ng/g (limit of quantitation, LOQ)to 57.0 ng/g. Serum PFOS concentrations ranged from <6.1 ng/mL (LOQ) to 58.3 ng/mL. Among the 23 paired samples, the mean liver to serum ratio was 1.3:1 (95% confidence interval 0.9:1-1.7:1). This liver to serum ratio is comparable to that reported in a toxicological study of cynomolgus monkeys, which had liver and serum concentrations 2-3 orders of magnitude higher than observed in these human donors. This information may be useful in human risk characterization for PFOS. Liver to serum ratios were not estimated for PFOA, PFHxS, and PFOSA as 90% of the human donor liver samples were determined to be less than the LOQ.     

Association between perfluorinated compounds and pathological conditions in southern sea otters

Concentrations of four perfluorinated contaminants, including perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), were measured in liver tissue from 80 adult female sea otters collected from the California coast during 1992-2002. Concentrations of PFOS and PFOA were in the ranges of <1-884 and <5-147 ng/g, wet wt, respectively. Concentrations of PFOA in the livers of these sea otters were among the highest values reported for marine mammals to date. Liver tissue from 6 male sea otters also was analyzed and contained significantly higher concentrations of PFOS than did tissues from female otters. To examine the association between exposures and potential effects, concentrations of PFOS and PFOA were compared among the adult female otters that died from infectious diseases, noninfectious causes, and from apparent emaciation. Concentrations of both PFOA and PFOS were significantly higher in sea otters in the infectious disease category than in the noninfectious category. Concentrations of PFOS and PFOA were not significantly different between noninfectious and emaciated otters, suggesting that the poor nutritive (body) status of emaciated otters did not affectthe concentrations of perfluorochemicals in livers. Concentrations of PFOA increased significantly from 1992 to 2002, whereas PFOS concentrations increased from 1992to 1998 and then decreased after 2000. Significant association between infectious diseases and elevated concentrations of PFOS/PFOA in the livers of sea otters is a cause for concern and suggests the need for further studies.     

Total mercury levels in muscle tissue of swordfish (Xiphias gladius) and bluefin tuna (Thunnus thynnus) from the Mediterranean Sea (Italy).

This study was carried out to determine the current levels of total mercury in the muscle tissue of swordfish (Xiphias gladius) and bluefin tuna (Thunnus thynnus) caught in the Mediterranean Sea with the purpose of ascertaining whether the concentrations exceeded the maximum level fixed by the European Commission Decision. In addition, specimens of each species were divided into different ranges of weight to investigate the influence of size on mercury accumulation in order to provide data upon which commercial fishing strategies and marketing of swordfish and bluefin tuna may be based. Higher mean levels of total mercury were found in bluefin tuna (1.02 microg g(-1) wet wt) than in swordfish (0.49 microg g(-1) wet wt). In 4.3% of swordfish and in 44.3% of bluefin tuna analyzed, total mercury concentrations exceeded the maximum level fixed by the European Commission Decision (Hg = 1 microg g(-1) wet wt). Besides, for bluefin tuna the total mercury level variability observed, due to size, suggests that there should be greater regulatory control by the authorities.     

Monitoring of perfluorinated compounds in edible fish from the Mediterranean Sea

Perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) are environmental contaminants belonging to a chemical group known as perfluorinated compounds (PCFs). The United States Environmental Protection Agency (US EPA) considers both compounds to be carcinogenic. The goal of the present study was to evaluate the contamination levels of PFOS and PFOA in edible fish of the Mediterranean Sea. Twenty six fish muscles, 17 fish livers, five series of cephalopods (each composed of ten specimens) and thirteen series of bivalves (each composed of about 50 specimens) were used for the investigation. A fast sample treatment, followed by an LC–ESI–MS/MS method is described for the identification, and quantification of PFOA and PFOS in fish. The method was in-house-validated through the determination of precision, accuracy, specificity, calibration curve, decision limit (CCα), and detection capability (CCβ). The results showed PFOA and PFOS levels in fishes and molluscs lower than those reported for analogue matrices in different geographic areas. Therefore, our biomonitoring results did not show that the Mediterranean Sea had any particularly alarming pollution by PFCs, although it is located in a semi-closed basin with scarce water change. Nonetheless, a worrying element is that a few fish showed extremely high contamination by PFOA and PFOS. This finding needs further clarification in order to assess whether such unusual contamination is linked to “dot-like” pollutant release, which could explain the anomaly.     

Perfluorinated Alkyl Acids in Blood Serum from Primiparous Women in Sweden: Serial Sampling during Pregnancy and Nursing, And Temporal Trends 1996-2010

We investigated temporal trends of blood serum levels of 13 perfluorinated alkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in primiparous women (N = 413) from Uppsala County, Sweden, sampled 3 weeks after delivery 1996-2010. Levels of the short-chain perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS) increased 11%/y and 8.3%/y, respectively, and levels of the long-chain perfluorononanoate (PFNA) and perfluorodecanoate (PFDA) increased 4.3%/y and 3.8%/y, respectively. Concomitantly, levels of FOSA (22%/y), perfluorooctane sulfonate (PFOS, 8.4%/y), perfluorodecane sulfonate (PFDS, 10%/y), and perfluorooctanoate (PFOA, 3.1%/y) decreased. Thus, one or several sources of exposure to the latter compounds have been reduced or eliminated, whereas exposure to the former compounds has recently increased. We explored if maternal levels of PFOS, PFOA, and PFNA during the early nursing period are representative for the fetal development period, using serial maternal serum samples, including cord blood (N = 19). PFAA levels in maternal serum sampled during pregnancy and the nursing period as well as in cord blood were strongly correlated. Strongest correlations between cord blood levels and maternal levels were observed for maternal serum sampled shortly before or after the delivery (r = 0.70-0.89 for PFOS and PFOA). A similar pattern was observed for PFNA, although the correlations were less strong due to levels close to the method detection limit in cord blood.     

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.     

Health risks in infants associated with exposure to perfluorinated compounds in human breast milk from Zhoushan, China

Recent studies have reported the ubiquitous distribution of perfluorinated compounds (PFCs), especially perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), in wildlife and human whole blood or serum. In 2003 a solid phase extraction method was developed, which allowed the measurement of PFCs in human breast milk. In the present study, PFCs in samples of human breast milk from 19 individuals from Zhoushan, China, were analyzed by modifying a previously established method, based on weak-anion exchange extraction. PFOS and PFOA were the two dominant chemicals detected in all the milk samples. Concentrations of PFOS and PFOA ranged from 45 to 360 ng/L and 47 to 210 ng/L, respectively. The maximum concentrations of other PFCs were 100 ng/L for perfluorohexanesulfonate (PFHxS), 62 ng/L for perfluorononanoate (PFNA), 15 ng/L for perfluorodecanoate (PFDA) and 56 ng/L for perfluoroundecanoate (PFUnDA). Statistically significant correlations between various PFCs suggested a common exposure source to humans. No statistically significant correlation was found between concentrations of either PFOS or PFOA and maternal age, weight, or infant weight. Rate of consumption of fish was found to be positively correlated with PFNA, PFDA, and PFUnDA concentrations. Daily intake of PFOS for the child via breast milk with greater PFOS concentrations exceeded the predicted conservative reference dose in 1 of 19 samples, indicating that there may be a small potential risk of PFOS for the infants in Zhoushan via the consumption of breast milk.     

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.     

Occurrence and sources of perfluorinated surfactants in rivers in Japan

We analyzed perfluorinated surfactants (PFSs) in 20 river samples and 5 wastewater secondary effluent samples in Japan to reveal their occurrence and sources. Nine PFS species were determined: perfluorooctanesulfonate (PFOS), perfluorooctane sulfonamide (FOSA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), perfluorododecanoate (PFDDA), and perfluorotridecanoate (PFTDA). PFSs were detected in all rivers, revealing nationwide contamination of rivers. In particular, 11 out of 20 river samples exceeded New Jersey guidance for PFOA in drinking water (40 ng/L). PFOS, PFHpA, PFOA, and PFNA were major species in Japan. Concentrations of PFOS, PFHpA, and PFNA in rivers were strongly correlated with population density, suggesting that the chemicals were derived from urban activities. PFOA showed a significant but weak correlation. We used crotamiton, a marker of sewage effluent, for further source analysis. Concentrations of PFOS, PFHpA, and PFNAwere strongly correlated with those of crotamiton, and plots of secondary effluents fell near the regression lines of rivers, indicating that the PFOS, PFHpA, and PFNA in rivers were derived from sewage effluent. On the other hand, PFOA was found at remarkably high levels (54-192 ng/L) in seven river samples containing low levels of crotamiton, suggesting that it was derived from nonsewage point sources, as well as sewage effluent. The total fluxes of sewage-derived PFOS, PFHpA, PFOA, and PFNA from Japan were estimated to be 3.6, 2.6, 5.6, and 2.6 t/year, respectively. This is the first report to identify PFOA in several rivers, derived from nonsewage point sources, by using a marker of sewage effluent.     

Detection of perfluorooctane surfactants in Great Lakes water

Widespread use of perfluorooctane surfactants has led to ubiquitous presence of these chemicals in biological tissues. While perfluorooctane surfactants have been measured in blood and liver tissue samples of fish, birds, and mammals in the Great Lakes region, data for the aqueous concentrations of these compounds in the Great Lakes or other ambient waters is lacking. Sixteen Great Lakes water samples were analyzed for eight perfluorooctane surfactants. The monitored perfluorooctane surfactants were quantitatively determined using single quadrupole HPLC/MS and qualitatively confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively confirmed using triple quadrupole LC/MS/MS. Concentrations of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50 ng/L, respectively. Analysis also showed the presence of PFOS precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate, another precursor, was identified at six of eight locations with a concentration range, when present, of <2.2-17 ng/L. Other PFOS precursors, N-EtFOSE, PFOSAA, and N-EtFOSA were not observed at any of the sampling locations. These are the first reported concentrations of perfluorooctane surfactants in Great Lakes water and the first report of PFOS precursors in any water body.     

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。