Abstract  Perfluorooctane sulfonate (PFOS) has been reported to be among the most concentrated persistent organic pollutants in Arctic marine wildlife. The present study examined the in vitro depletion of major PFOS precursors, N-ethyl-perfluorooctane sulfonamide (N-EtFOSA) and perfluorooctane sulfonamide (FOSA), as well as metabolite formation using an assay based on enzymatically viable liver microsomes for three top Arctic marine mammalian predators, polar bear (Ursus maritimus), beluga whale (Delphinapterus leucas), and ringed seal (Pusa hispida), and in laboratory rat (Rattus rattus) serving as a general mammalian model and positive control. Rat assays showed that N-EtFOSA (38 nM or 150 ng mL(-1)) to FOSA metabolism was >90% complete after 10 min, and at a rate of 23 pmol min(-1) mg(-1) protein. Examining all species in a full 90 min incubation assay, there was >95% N-EtFOSA depletion for the rat active control and polar bear microsomes, similar to 65% for ringed seals, and negligible depletion of N-EtFOSA for beluga whale. Concomitantly, the corresponding in vitro formation of FOSA from N-EtFOSA was also quantitatively rat approximate to polar bear > ringed seal >>> beluga whale. A lack of enzymatic ability and/or a rate too slow to be detected likely explains the lack of N-EtFOSA to FOSA transformation for beluga whale. In the same assays, the depletion of the FOSA metabolite was insignificant (p > 0.01) and with no concomitant formation of PFOS metabolite. This suggests that, in part, a source of FOSA is the biotransformation of accumulated N-EtFOSA in free-ranging Arctic ringed seal and polar bear.

Abstract  A pre-sampling isotope dilution-direct injection-liquid chromatography tandem mass spectrometry (DI-LC/MS/MS) analytical method for the analysis of perfluorinated compounds (PFCs) in water is presented. This pre-sampling isotope dilution method incorporates stable isotope internal standards (ISs) and surrogate recovery standards (SRSs) added to sample bottles prior to sample collection. Pre-sampling isotope dilution corrects for PFC adsorption losses and enables a simple quantitative DI-LC/MS/MS water method with a 28 day sample holding time. Method analytes include perfluorinated carboxylic acids (PFCAs) (C4-C12), perfluorinated sulfonic acids (PFSAs) (C4, C6, and C8), perfluorooctane sulfonamide (PFOSA), and four SRSs ([2,3,4-C-13(3)]PFBA, [1,2,3,4-C-13(4)]PFOA, [1,2,3,4-C-13(4)]PFOS, and [1,2-C-13(2)]PFUnA). At 28 day sample holding times, mean recoveries of laboratory reagent water samples (Milli-Q (TM) water containing hardness at 165 mg equivalent CaCO3 L-1) fortified with the PFC method analytes at 0.2-40 ng mL(-1) (0.1-1 ng mL(-1) SRSs) are 94.9-115% with relative standard deviations of 0.97-7.9%. At 28 day sample holding times in fortified laboratory reagent water samples, single laboratory lowest concentration minimum reporting levels of 0.010-0.020 ng mL(-1) (0.075 ng mL(-1) PFBA) are demonstrated for method analytes and SRSs. Method applications to synthetic chlorinated drinking water samples and three environmental sample matrices are presented that demonstrate method ruggedness. Mean recoveries of synthetic chlorinated drinking water samples fortified with the PFC method analytes at 0.1-10 ng mL(-1) and SRSs at 0.1-1 ng mL(-1) are 97.8-113% with relative standard deviations of 2.0-18%. Mean recoveries and relative standard deviations in environmental groundwater samples, production facility non-contact cooling water effluent samples, and production facility wastewater treatment effluent samples fortified with the PFC method analytes at 0.25-2.5 ng mL(-1), 0.25-10 ng mL(-1), 0.25-50 ng mL(-1) respectively and SRSs at 0.1 ng mL(-1) are 100 +/- 7.7% (RSD +/- 12%, PFBA +/- 23%), 100 +/- 5.5% (RSD +/- 11%), 100 +/- 5.2% (RSD +/- 11%) respectively. Excellent method correlation was obtained with USEPA Method 537 in a comparative analysis of synthetic chlorinated drinking water samples aged 7 days and fortified with C6-C12 PFCAs and C4, C6, and C8 PFSAs, and three SRSs [C-13(4)] PFOA, [C-13(2)] PFUnA, and [C-13(4)] PFOS at 0.1 ng mL(-1). The average absolute difference between the EPA Method 537 and DI-LC/MS/MS measurements for the method analytes and SRSs was 8%.

Abstract  The continuous production and use in certain parts of the world of perfluoroalkyl sulfonamide derivatives that can degrade to perfluorooctane sulfonic acid (PFOS) has called for better understanding of the environmental fate of these PFOS precursors. Aerobic soil biotransformation of N-ethyl perfluorooctane sulfonamide (EtFOSA, also known as Sulfluramid) was quantitatively investigated in semi-closed soil microcosms over 182 d for the first time. The apparent soil half-life of EtFOSA was 13.9±2.1 d and the yield to PFOS by the end of incubation was 4.0 mol%. A positive identification of a previously suspected degradation product, EtFOSA alcohol, provided strong evidence to determine degradation pathways. The lower mass balance in sterile soil than live soil suggested likely strong irreversible sorption of EtFOSA to the test soil. The aerobic soil biotransformation of a technical grade N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) was semi-quantitatively examined, and the degradation pathways largely followed those in activated sludge and marine sediments. Aside from PFOS, major degradation products included N-Ethyl perfluorooctane sulfonamidoacetic acid (EtFOSAA), perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonamide acetic acid (FOSAA). This study confirms that aerobic soil biotransformation of EtFOSE and EtFOSA contributes significantly to the PFOS observed in soil environment, as well as to several highly persistent sulfonamide derivatives frequently detected in biosolid-amended soils and landfill leachates.

Abstract  Objective: We established a method of UPLC-MS/MS that was to detect fifteen precursors of perfluoroalkyl sulfonates (PFSA) and perfluoroalkyl carboxylates (PFCA) in serum. Methods: Briefly, TBAS solution was added to sera, then the mixed solution was extracted with aliquots of MTBE. The MTBE aliquots were combined, evaporated to dryness under nitrogen, and reconsituted in 0.25 ml of methanol and water (1:1). Then the reconstituted solution through 0.2 µm nylon syringe filter was collected. Chromatographic separation was performed using a Waters ACQUITY (TM) BEH ¹⁸C column (50 mm × 2.1 mm × 1.7 mm). Analyte quantitation was performed in the negative electrospray ionization mode and multiple reaction monitoring (MRM). Results: Three target substances, 6: 6PFPi, 6: 8PFPi, 8: 8PFPi, were externally confirmed by standard addition. Rates of recovery for these three chemicals were from 41.01% to 112.13% in two standard levels. And the relative standard deviations (RSD) were lower than 11.63% and higher than 1.80%. The other twelve substances were quantified with internal standard. Moreover in two standard levels, rate of recovery for these chemicals ranged from 70.25% to 127.51%. And RSD were more than 1.23% and less than 15.45%. And the corresponding limit of detection (LOD) and limit of quantitation (LOQ) for all target substances were 0.1-5.0 pg/ml and 0.2-10.0 pg/ml. Then we detected these target substances in ten different human serum samples. The levels of few substances were higher than LOD. And the ranges of FOSA-M, N-EtFOSA-M, N-MeFOSAA, N-EtFOSAA were respectively < LOD-0.94 pg/ml, < LOD-10.08 pg/ml, < LOD-6.74 pg/ml, < LOD-1.04 pg/ml. Conclusion: The method, with high sensitivity and accuracy, could meet the actual testing requirements.

Abstract  We have investigated the effects of perfluorooctane sulfonamide (PFOSA) on cellular functions and lipid homeostasis (including beta-oxidation) in salmon primary hepatocytes. Salmon hepatocytes were exposed to PFOSA at 0 (control), 2, 20, and 50 mu M for 12 and 24 h. Fatty acids (FM) and lipids were determined by GC-MS; FA elongase (FAE), Delta 5-desaturase (FADS), Delta 6-desaturase (FAD6), peroxisome proliferator-activated receptors (PPARs), acyl coenzyme A (ACOX-1), glutathione peroxidase (GPx), catalase (CAT), and glutathione S-transferase (GST) mRNA were analyzed using qPCR. GST activity was analyzed by biochemical assays using 1-chloro-2,4-dinitrobenzene (CDNB) as substrate. Our data showed that PFOSA produced significant changes in FA composition that predominantly involved a decrease (at 12 h) and an increase (at 24 h) in FA methyl esters (FAMEs), MUFA, total PUFA, and (n-3 and n-6) PUFA. Particularly, an increase of alpha-linolenic acid (ALA; 18:3n-3), eicosapentaenoic acid [EPA; 20:5n-3], and arachidonic acid [ARA: 20:4n-6] with associated increase in FAE, FADS, and FAD6 mRNA were observed after PFOSA exposure, while cis-13,16-docosadienoic acid (22:2) was significantly decreased. PFOSA produced apparent concentration-dependent increase of PPAR alpha and PPAR gamma. CAT, GPx, and GST mRNA show that PFOSA produced concentration- and time-specific increase of CAT and GST, but no changes in GST activity were observed. In general, these responses indicate that PFOSA evokes deleterious effects on cellular lipid homeostasis a;ad transcriptional responses that regulate cellular oxidative homeostasis in salmon hepatocytes.

Abstract  Twenty high-volume air samples were collected during a crossing of the North Atlantic and Canadian Archipelago in July 2005 to investigate air concentrations of fluorotelomer alcohols (FTOHs) and perfluoalkyl sulfonamido ethanols (PFASs). These commercial chemicals are widely used as surface treatments and are believed to be precursors for perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) that accumulate in humans and biota, including those from remote arctic regions. The highest concentrations (sum of gas- and particle-phase) of FTOHs were for 8:2 FTOH (perfluoroctyl ethanol) (5.8-26 pg/m(3)), followed by 10:2 FTOH (perfluorodecyl ethanol) (1.9-17 pg/ m(3)) and 6:2 FTOH (perfluorohexyl ethanol) [BDL (below detection limit) to 6.0 pg/m(3)]. For the PFASs, MeFOSE (N-methyl perfluorooctane sulfonamido ethanol) was dominant and ranged from 2.6 to 31 pg/m(3); EtFOSE (N-ethyl perfluorooctane sulfonamido ethanol) ranged from BDL to 8.9 pg/m(3) and MeFOSEA (N-methyl perfluorooctane sulfonamide ethylacrylate) was BDL in all samples. Air parcel back-trajectories showed that the sampled air was largely representative of the arctic air mass. Air concentrations of target compounds were of the same order of magnitude as reported air concentrations in source regions. For instance, the mean 8:2 FTOH concentration was only a factor of about 3 lower than for three urban samples that were collected in Toronto for comparison. These findings confirm model results that predictthe efficient, long-range atmospheric transport and widespread distribution of FTOHs and related compounds in the arctic region. Mean particulate percentages for FTOHs and PFASs in the cruise samples (mean temperature, 5+/-4 degrees C) were BDL for 6:2 FTOH, 23% for 8:2 FTOH, 15% for 10:2 FTOH, 32% for MeFOSE, and 22% for EtFOSE. Further, the partitioning to particles for MeFOSE and EtFOSE was significantly correlated with inverse absolute temperature, whereas the FTOHs did not show this trend. The Toronto samples (mean temperature, -1+/-1 degree C) showed similar particulate percentages for MeFOSE and EtFOSE; however, the FTOHs were substantially less particle-bound. Although the mechanism for this partitioning is not understood, the results do indicate the need to better account for particle phase transport when modeling the atmospheric fate of these chemicals.

Abstract  In this study, we analyzed over 30 types of PFCs, including precursors in both the dissolved phase and particle solid phase, in 50 samples of river water collected from throughout the Tokyo Bay basin. PFCs were detected in suspended solids (SSs) at levels ranging from <0.003-4.4 ng L(-1) (0.11-2470 ng g(-1) dry weight). The concentrations of PFCs in the SS were one to two order(s) of magnitude lower than those of PFCs in the dissolved phase. Relatively high levels of PFCs (total of 35 PFCs) in SS were observed in urbanized areas. The concentration of PFCAs, including PFOA and PFNA, were significantly correlated with the geographic index as artificial area (R(2) of the linear regression curve in a double logarithmic plot: 0.09-0.55). Conversely, PFOS and FOSA were significantly correlated with the arterial traffic area (R(2) in a double logarithmic plot: 0.29-0.55). Those spatial trends were similar to the trends in dissolved PFCs. We estimated the loading amount of PFCs into Tokyo Bay from six main rivers and found that more than 90% of the total PFCs reached Tokyo Bay in the dissolved phase. However, 40.0-83.5% of the long chain PFCAs (C12-C15), were transported as particle sorbed PFCs. Rain runoff events might increase the loading amount of PFCs in SS. Overall, the results presented herein indicate that greater attention should be given to PFCs, especially for longer chain PFCs in SS in addition to dissolved PFCs.

Abstract  Introduction Polyfluoroalkyl chemicals (PFCs) are commercially synthesized chemicals used in consumer products. Exposure to certain PFCs is widespread, and some PFCs may act as endocrine disruptors. We used data from the Avon Longitudinal Study of Parents and Children (ALSPAC) in the United Kingdom to conduct a nested case-control study examining the association between age at menarche, and exposure to PFCs during pregnancy. Methods Cases were selected from female offspring in the ALSPAC who reported menarche before the age of 11.5 years (n = 218), and controls were a random sample of remaining girls (n = 230). Serum samples taken from the girls' mothers during pregnancy (1991–1992) were analyzed using on-line solid-phase extraction coupled to isotope dilution high-performance liquid chromatography-tandem mass spectrometry for 8 PFCs. Logistic regression was used to determine association between maternal serum PFC concentrations, and odds of earlier age at menarche. Results PFOS and PFOA were the predominant PFCs (median serum concentrations of 19.8 ng/mL and 3.7 ng/mL). All but one PFC were detectable in most samples. Total PFC concentration varied by number of births (inverse association with birth order; p-value < 0.0001) and race of the child (higher among whites; p-value = 0.03). The serum concentrations of carboxylates were associated with increased odds of earlier age at menarche; concentrations of perfluorooctane sulfonamide, the sulfonamide esters and sulfonates were all associated with decreased odds of earlier age at menarche. However, all confidence intervals included the null value of 1.0. Conclusions ALSPAC study participants had nearly ubiquitous exposure to most PFCs examined, but PFC exposure did not appear to be associated with altered age at menarche of their offspring.

Abstract  Concentrations of 19 perfluorochemicals have been quantified in human blood and in some marine food resources from the region of the Gulf of Gdañsk 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.

Abstract  Perfluorooctanesulfonyl fluoride (POSF, C8F17SO2F) related-materials have been used as surfactants, paper and packaging treatments, and surface (e.g., carpet, textile, upholstery) protectants. A metabolite, perfluorooctanesulfonate (PFOS, C8F17SO3-), has been identified in the serum and liver of non-occupationally exposed humans and wildlife. Because of its persistence, an important question was whether elderly humans might have higher PFOS concentrations. From a prospective study designed to examine cognitive function in the Seattle (WA) metropolitan area, blood samples were collected from 238 dementia-free subjects (ages 65-96). High-pressure liquid chromatography-electrospray tandem mass spectrometry determined seven fluorochemicals: PFOS; N-ethyl perfluorooctanesulfonamidoacetate; N-methyl perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamide; perfluorooctanoate; and perfluorohexanesulfonate. Serum PFOS concentrations ranged from less than the lower limit of quantitation (3.4 ppb) to 175.0 ppb (geometric mean 31.0 ppb; 95% CI 28.8-33.4). An estimate of the 95% tolerance limit was 84.1 ppb (upper 95% confidence limit 104.0 ppb). Serum PFOS concentrations were slightly lower among the most elderly. There were no significant differences by sex or years residence in Seattle. The distributions of the other fluorochemicals were approximately an order of magnitude lower. Similar to other reported findings of younger adults, the geometric mean serum PFOS concentration in non-occupational adult populations likely approximates 30-40 ppb with 95% of the population's serum PFOS concentrations below 100 ppb.

Abstract  Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.

Abstract  Semivolatile fluorinated organic compounds (FOCs) were measured in archived air sample extracts collected from Hedo Station Observatory (HSO) on Okinawa, Japan and Mount Bachelor Observatory (MBO), Oregon U.S. during the springs of 2004 (MBO and HSO) and 2006 (MBO). Fluorotelomer alcohols (FTOHs) were measured in both Asian and western U.S. air masses, though western U.S. air masses had significantly higher concentrations. Concentrations of fluorotelomer olefins in Asian air masses and 8:2 fluorotelomer acrylate in U.S. air masses were reported for the first time. N-ethyl perfluorooctane sulfonamide, N-methyl perfluorooctane sulfonamido ethanol, and N-ethyl perfluorooctane sulfonamido ethanol were also measured in Asian and western U.S. air masses but less frequently than FTOHs. The atmospheric sources and fate of FTOHs were investigated by estimating their atmospheric residence times, calculating FTOH concentration ratios, investigating FTOH correlations with nonfluorinated semivolatile organic compound concentrations, and determining air mass back trajectories. Estimated atmospheric residence times for 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH were 50, 80, and 70 d, respectively, and the average concentration ratio of 6:2 FTOH to 8:2 FTOH to 10:2 FTOH at MBO in 2006 was 1.0 to 5.0 to 2.5. The relative order of these atmospheric residence times may explain the observed enhancement of 8:2 FTOH and 10:2 FTOH (relative to 6:2 FTOH) at MBO compared to North American indoor air (FTOH average ratio of 1.0 to 2.0 to 1.0). FTOH concentrations in western U.S. air masses were positively correlated (p < 0.05) with gas-phase polycyclic aromatic hydrocarbon and polychlorinated biphenyl concentrations and negatively correlated (p < 0.05) with agricultural pesticide concentrations. In comparison to western U.S. air masses, trans-Pacific air masses did not contain elevated concentrations of these compounds, whereas lower boundary layer air masses that passed over urban areas of the western U.S. did. This suggests that semivolatile FOCs are emitted from urban areas in the western U.S.

Abstract  Perfluorochemicals (PFCs) are the subject of increasingly intense environmental research. Despite their detection both in biota and in aqueous systems, little attention has been paid to the possible presence of this class of compounds in solid environmental matrixes. The limited available data indicate that some PFCs such as perfluorooctane sulfonate (PFOS) may strongly sorb to solids, and sewage sludge is widely suspected as a major sink of PFCs entering municipal waste streams. A quantitative analytical method was developed that consists of liquid solvent extraction of the analytes from sediments and sludge, cleanup via solid-phase extraction, and injection of the extracts with internal standards into a high-performance liquid chromatography (HPLC) system coupled to a tandem mass spectrometer (LC/MS/MS). The limits of detections of the method were analyte and matrix dependent, but ranged from 0.7 to 2.2 ng/g and 0.041 to 0.246 ng/g (dry weight) for sludge and sediment, respectively. A demonstration of the method was performed by conducting a limited survey of domestic sludge and sediments. The concentration of PFCs in domestic sludge ranged from 5 to 152 ng/g for total perfluorocarboxylates and 55 to 3370 ng/g for total perfluoroalkyl sulfonyl-based chemicals. Data from a survey of San Francisco Bay Area sediments suggest widespread occurrence of PFCs in sediments at the low ng/g to sub-ng/g level. Furthermore, substances that may be transformed to PFOS, such as 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA) and 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), are present in both sediments and sludge at levels often exceeding PFOS.

Abstract  BACKGROUND: Perfluoroalkyl acids are persistent compounds used in various industrial -applications. Of these compounds, perfluorooctanoate (PFOA) is currently detected in humans worldwide. A recent study on low-dose developmental exposure to PFOA in mice reported increased weight and elevated biomarkers of adiposity in postpubertal female offspring.

OBJECTIVE: We examined whether the findings of increased weight in postpubertal female mice could be replicated in humans.

METHODS: A prospective cohort of 665 Danish pregnant women was recruited in 1988-1989 with offspring follow-up at 20 years. PFOA was measured in serum from gestational week 30. Offspring body mass index (BMI) and waist circumference were recorded at follow-up (n = 665), and biomarkers of adiposity were quantified in a subset (n = 422) of participants.

RESULTS: After adjusting for covariates, including maternal pre-pregnancy BMI, smoking, education, and birth weight, in utero exposure to PFOA was positively associated with anthropometry at 20 years in female but not male offspring. Adjusted relative risks comparing the highest with lowest quartile (median: 5.8 vs. 2.3 ng/mL) of maternal PFOA concentration were 3.1 [95% confidence interval (CI): 1.4, 6.9] for overweight or obese (BMI ≥ 25 kg/m2) and 3.0 (95% CI: 1.3, 6.8) for waist circumference > 88 cm among female offspring. This corresponded to estimated increases of 1.6 kg/m2 (95% CI: 0.6, 2.6) and 4.3 cm (95% CI: 1.4, 7.3) in average BMI and waist circumference, respectively. In addition, maternal PFOA concentrations were positively associated with serum insulin and leptin levels and inversely associated with adiponectin levels in female offspring. Similar associations were observed for males, although point estimates were less precise because of fewer observations. Maternal perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (PFOSA), and perfluorononanoate (PFNA) concentrations were not independently associated with offspring anthropometry at 20 years.

CONCLUSIONS: Our findings on the effects of low-dose developmental exposures to PFOA are in line with experimental results suggesting obesogenic effects in female offspring at 20 years of age.

Abstract  Per- and poly-fluorinated compounds (PFCs), which include perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) and various precursors, are used in a wide variety of industrial, commercial and domestic products. This includes aqueous film forming foam (AFFF), which is used by military and commercial airports as fire suppressants. In a preliminary assessment prior to this study, very high concentrations (>1 ppm wet weight) of the PFSA, perfluorooctane sulfonate (PFOS), were discovered in the plasma of snapping turtles (Chelydra serpentina) collected in 2008 from Lake Niapenco in southern Ontario, Canada. We presently report on a suite of C(6) to C(15) PFCAs, C(4), C(6), C(8) and C(10) PFSAs, several PFC precursors (e.g. perfluorooctane sulfonamide, PFOSA), and a cyclic perfluorinated acid used in aircraft hydraulic fluid, perfluoroethylcyclohexane sulfonate (PFECHS) in surface water from the Welland River and Lake Niapenco, downstream of the John C. Munro International Airport, Hamilton, Ontario, Canada. Amphipods, shrimp, and water were sampled from the Welland River and Lake Niapenco, as well as local references. The same suite of PFCs in turtle plasma from Lake Niapenco was compared to those from other southern Ontario sites. PFOS dominated the sum PFCs in all substrates (e.g., >99% in plasma of turtles downstream the Hamilton Airport, and 72.1 to 94.1% at all other sites). PFOS averaged 2223(±247.1SE) ng/g in turtle plasma from Lake Niapenco, and ranged from 9.0 to 171.4 elsewhere. Mean PFOS in amphipods and in water were 518.1(±83.8)ng/g and 130.3(±43.6) ng/L downstream of the airport, and 19.1(±2.7) ng/g and 6.8(±0.5) ng/L at reference sites, respectively. Concentrations of selected PFCs declined with distance downstream from the airport. Although there was no known spill event or publicly reported use of AFFF associated with a fire event at the Hamilton airport, the airport is a likely major source of PFC contamination in the Welland River.

Abstract  Spatial trends of concentrations of perfluorinated chemicals (PFCs) were investigated in harbour seal liver tissue from seven locations in Denmark, ranging from the Wadden Sea in the southern North Sea to the Western Baltic. All samples were collected during the phocine distemper epizootic in 2002 which provided access to a large number of comparable samples over a short time period. PFOS was dominating (mean: 92% of ∑PFC) among the PFCs in the samples, followed by considerably lower concentrations of PFHxS (1.8%), PFDA (1.7%), PFNA (1.6%) PFUnA (1.5%), PFOA (0.9%) and PFOSA (0.5%). The concentrations of all the investigated compounds showed significant differences among the seven locations. PFOS showed the highest concentrations in the Wadden Sea, where high burdens have also been recorded in German seals. Most compounds showed a trend towards higher concentrations at one or both extremes of the geographic range. Two different patterns of relative PFC concentrations were detected; one in the inner Danish waters where PFOSA and PFUnA were more prevalent and another in the Wadden Sea and Limfjord where PFOA, PFHxS and PFNA were found in greater proportions. These patterns probably represent Baltic and North Sea contamination sources.

Abstract  Perfluorooctanesulfonate (PFOS) at 1.6-39 ng/g ww and 4.8-200 pg/mL, respectively, perfluorooctanoate (PFOA) at 0.06-0.28 ng/g ww and<0.05-1.8 pg/mL, and perfluorodecanoate (PFDA) at 0.13-0.57 ng/g ww and 0.05-1.8 pg/mL, were detected in all specimens of European Beaver's (Castor fiber) liver as well as in whole blood of Cod (Gadus morhua), Velvet Scoter (Melanitta fusca), Eider Duck (Sommateria mollisima), Long-tailed Duck (Clangula hyemalis), Razorbill (Alca torda), Red-throated Diver (Gavia stellata) sampled in Poland. At smaller concentrations and at less frequency was perfluorononanoate (PFNA) at 0.05-1.4 ng/g ww and<0.2-2 pg/mL, perfluorohexanoate (PFHxA) at 0.03-0.23 ng/g ww and<0.05-0.69 pg/mL, while perfluorohexanesulfonate (PFHxS) at 0.05-4.3 pg/mL and perfluorooctanesulfonamidoacetate (PFOSA) at 0.1-13 pg/mL were also found in Cod as well as in molluscivorous diving-ducks and fish-eating birds but not in Beaver, while perfluoroheptanoate (PFHpA) at<0.05-0.74 pg/mL was found only in Cod.

Abstract  This study reports the effect of a nonionic perfluorinated surfactant, N-polyoxyethylene-N-propyl perfluorooctane sulfonamide (PFOSA), as additive of background electrolyte on capillary electrophoresis (CE) of common inorganic cations. The association constants (K sub(ass)) for PFOSA estimated from the electrophoretic mobility of analyte cations were the order of Mg super(2+) > Ca super(2+) > Sr super(2+) >> K super(+) approximately NH super(+) sub(4) > Na super(+) approximately Li super(+). The K sub(ass) values were larger than those for zwitterionic and nonionic surfactants with hydrocarbon moiety. Use of PFOSA made another essential contribution to the determination of inorganic cations in a protein-containing sample. This was considered because high solubility of PFOSA for proteins functioned as suppressor for protein adsorption to the capillary wall. Four inorganic cations, Na super(+), K super(+), Mg super(2+), and Ca super(2+), in human saliva sample were successfully determined by sample injection without any pretreatments except for filtration and dilution.

Abstract  A well-defined subsample of 128 subadult (3-5 years) polar bears (Ursus maritimus) from 19 sampling years within the period 1984-2006 was investigated for perfluoroalkyl contaminants (PFCs), Linear regression analysis of logarithmic-transformed median concentrations showed significant annual increases for PFOS (4.7%), PFNA (6.1%), PFUnA (5.9%), PFDA (4.3%), PFTrA (8.5%), PFOA (2.3%), and PFDoA (5.2%). For four of the PFCs, a LOESS smoother model provided significantly better descriptions, revealing steeper linear annual increases for PFOSA of 9.2% after 1990 and between 18.6 and 27.4% for PFOS, PFDA, and PFTrA after 2000. Concentrations of Sigma PFCs, by 2006, exceeded the concentrations of all conventional OHCs (organohalogen compounds), of which several have been documented to correlate with a number of negative health effects. If the PFC concentrations in polar bears continue to increase with the steepest observed trends, then the lowest no-adverse-effect level (NOAEL) and lowest-adverse-effect level (LOAEL) detected for rats and monkeys will be exceeded in 2014-2024. In addition, the rapidly increasing concentrations of PFCs are likely to cause cumulative and combined effects on the polar bear, compounding the already detected threats from OHCs.

Abstract  Fluorotelomer alcohols (FTOHs) and perfluorooctane sulfonamides (FOSAs) are present in consumer products and are semi-volatile precursors of persistent perfluoroalkyl acids (PFAAs). The high variability of levels of FTOHs and FOSAs in products makes it difficult to derive FTOH- and FOSA-emissions from urban areas based on emission factors. Here we used a multimedia mass balance model that describes the day-night cycle of semi-volatile organic chemicals in air to interpret measurements of 8:2 FTOH, 10:2 FTOH, MeFOSA and EtFOSA from a sampling campaign in summer 2010 in Zurich, Switzerland. The estimated emission source strength of the four substances follows the sequence: 8:2 FTOH (2.6 g/h) > 10:2 FTOH (0.75 g/h) > MeFOSA (0.08 g/h) > EtFOSA (0.05 g/h). There is no FTOHs- or FOSAs-related industry in Zurich. Accordingly, our estimates are representative of diffusive emissions during use and disposal of consumer products, and describe noticeable sources of these PFASs to the environment.

Abstract  Organic fluorochemicals are used in multiple commercial applications including surfactants, lubricants, paints, polishes, food packaging, and fire-retarding foams. Recent scientific findings suggest that several perfluorochemicals (PFCs), a group of organic fluorochemicals, are ubiquitous contaminants in humans and animals worldwide. Furthermore, concern has increased about the toxicity of these compounds. Therefore, monitoring human exposure to PFCs is important. We have developed a high-throughput method for measuring trace levels of 13 PFCs (2 per-fluorosulfonates, 8 perfluorocarboxylates, and 3 perfluorosulfonamides) in serum and milk using an automated solid-phase extraction (SPE) cleanup followed by high-performance liquid chromatography-tandem mass spectrometry. The method is sensitive, with limits of detection between 0.1 and 1 ng in 1 mL of serum or milk, is not labor intensive, involves minimal manual sample preparation, and uses a commercially available automated SPE system. Our method is suitable for large epidemiologic studies to assess exposure to PFCs. We measured the serum levels of these 13 PFCs in 20 adults nonoccupationally exposed to these compounds. Nine of the PFCs were detected in at least 75% of the subjects. Perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), 2-(N-methylperfluorooctanesulfonamido)acetate (Me-PFOSA-AcOH), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA) were found in all of the samples. The concentration order and measured levels of PFOS, PFOA, Me-PFOSA-AcOH, and PFHxS compared well with human serum levels previously reported. Although no human data are available for the perfluorocarboxylates (except PFOA), the high frequency of detection of PFNA and other carboxylates in our study suggests that human exposure to long-alkyl-chain perfluorocarboxylates may be widespread. We also found PFOS in the serum and milk of rats administered PFOS by gavage, but not in the milk of rats not dosed with PFOS. Furthermore, we did not detect most PFCs in two human milk samples. These findings suggest that PFCs may not be as prevalent in human milk as they are in serum. Additional studies are needed to determine whether environmental exposure to PFCs can result in PFCs partitioning into milk. Large epidemiological studies to determine the levels of PFCs among the U.S. general population are warranted.

Abstract  Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.

Abstract  Numerous studies have reported on the global distribution, persistence, fate, and toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFASs). However, studies on PFASs in terrestrial mammals are scarce. Rats can be good sentinels of human exposure to toxicants because of their habitat, which is in close proximity to humans. Furthermore, exposure data measured for rats can be directly applied for risk assessment because many toxicological studies use rodent models. In this study, a nationwide survey of PFASs in the blood of wild rats as well as surface water samples collected from rats' habitats from 47 prefectures in Japan was conducted. In addition to known PFASs, combustion ion chromatography technique was used for analysis of total fluorine concentrations in the blood of rats. In total, 216 blood samples representing three species of wild rats (house rat, Norway rats, and field mice) were analyzed for 23 PFASs. Perfluorooctanesulfonate (PFOS; concentration range <0.05-148 ng/mL), perfluorooctane sulfonamide (PFOSA; <0.1-157), perfluorododecanoate (<0.05-5.8), perfluoroundecanoate (PFUnDA; <0.05-51), perfluorodecanoate (PFDA; <0.05-9.7), perfluorononanoate (PFNA; <0.05-249), and perfluorooctanoate (PFOA) (<0.05-60) were detected >80 % of the blood samples. Concentrations of several PFASs in rat blood were similar to those reported for humans. PFSAs (mainly PFOS) accounted for 45 % of total PFASs, whereas perfluoroalkyl carboxylates (PFCAs), especially PFUnDA and PFNA, accounted for 20 and 10 % of total PFASs, respectively. In water samples, PFCAs were the predominant compounds with PFOA and PFNA found in >90 % of the samples. There were strong correlations (p < 0.001 to p < 0.05) between human population density and levels of PFOS, PFNA, PFOA, and PFOSA in wild rat blood.

Abstract  Temporal trends in perfluoroalkyl compounds (PFCs) were investigated in liver samples from two ringed seal (Phoca hispida) populations in the Canadian Arctic, Arviat (Western Hudson Bay) (1992, 1998, 2004, 2005) and Resolute Bay (Lancaster Sound) (1972, 1993, 2000, 2004, 2005). PFCs analyzed included C7-C15 perfluorinated carboxylates (PFCAs) and their suspected precursors, the 8:2 and 10:2 fluorotelomer saturated and unsaturated carboxylates (FTCAs, FTUCAs), C4, C6, C8, C10 sulfonates, and perfluorooctane sulfonamide (PFOSA). Liver samples were homogenized, liquid-liquid extracted with methyl tert-butyl ether, cleaned up using hexafluoropropanol, and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). C9-C15 PFCAs showed statistically significant increasing concentrations during 1992-2005 and during 1993-2005 at Arviat and Resolute Bay, respectively. Doubling times ranged from 19.4 to 15.8 years for perfluorododecanoate (PFDoA) to 10.0-7.7 years for perfluorononanoate (PFNA) at Arviat and Resolute Bay but were shorter when excluding the 2005 samples. Conversely, perfluorooctane sulfonate (PFOS) and PFOSA concentrations showed maximum concentrations during 1998 and 2000 at Arviat and Resolute Bay, with statistically significant decreases from 2000 to 2005. In the case of Arviat, two consecutive decreases were measured from 1998 to 2003 and from 2003 to 2005. PFOS disappearance half-lives for seals at Arviat and Resolute Bay were 3.2 and 4.6 years. These results indicate that the ringed seals and their food web are rapidly responding to the phase out of perfluorooctane sulfonyl fluoride based compounds by 3M in 2001. Further, the relatively short doubling times of the PFCAs and PFOS disappearance half-lives support the hypothesis of atmospheric transport as the main transport mechanism of PFCs to the arctic environment.

Abstract  Table S1. Chemical structure of the target compounds, internal standards used and % recovery. Table S2. Mobile phase gradient used for separation of FTOH and FOSA (Fraction 1). Table S3. Mobile phase gradient used for separation of PFSA, PFCA and FTUCA (Fraction 2). Table S4. Arithmetic mean concentration (± SE ng/g wet weight) of detectable PFCAs with carbon chain length varying from C8 to C15 in herring gull eggs (n=13) collected from 15 colonies in the Great Lakes in 2007. Figure S1: Proportions of PFHxS, PFOS and PFDS to ΣPFSA concentrations plotted using the first two principal components (PCs), PC1 and PC2. Figure S2: Correlation between PFOS and its precursor PFOSA (ng/g wet weight) in individual eggs from all colonies. Figure S3: Plots of ΣPFSA and ΣPFCA concentration (ng/g wet weight) in individual herring gulls eggs, colonies were grouped per lake. Figure S4: Plots of ΣPFCA and ΣPFSA concentrations (ng/g wet weight) versus trophic position based on individual herring gull eggs collected in 2001-2002 from Strachan Island, St. Lawrence River.