Abstract  Per- and polyfluoroalkyl substances (PFASs) are a class of compounds with unique chemical properties that have been shown useful in a wide variety of applications because they provide materials with reduced surface tension and exceptional non-stick properties. PFASs are commonly found in impregnation materials, coatings of papers and textiles, fire-fighting foams, pesticides, and cleaning agents. The potential for human exposure to PFASs is high because of their widespread distribution. The aim of this study was to investigate levels of PFASs in men and women from Sweden and to assess the influence of gender and parity among women. Levels of 13 PFASs were determined in plasma samples collected during 2001-2004 from 1016 (507 women) 70year-old participants from the population-based Prospective Study of the Vasculature in Uppsala Seniors (PIVUS). The PFASs studied were nine perfluorinated carboxylic acids (PFCAs), four perfluorinated sulfonic acids (PFSAs) and perfluorooctane sulfonamide (PFOSA). In addition, structural isomers of perfluorooctane sulfonic acid (PFOS) were determined in a subset of 398 individuals. The detection rates were high and the majority of the studied compounds were detected in more than 75% of the participants. Levels of the selected analytes were found to be similar to other studies of non-occupationally exposed populations. Gender differences were observed in levels of PFHpA which was higher in men, while PFHxS was higher in women. Parity among women was shown to have a minor effect on PFAS concentrations and we found primi- and multiparous women to have slightly lower levels of PFUnDA when compared to nulliparous women.

Abstract  This study provides the first evidence on the influence of the semiconductor and electronics industries on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs, including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs: PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic industrial wastewaters and their receiving water bodies (Taiwan's Keya, Touchien, and Xiaoli rivers). PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However, different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%). The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest concentrations (up to 5.4 microg/L).

Abstract  Transport and fate of perfluoro- and polyfluoroalkyl substances (PFASs) in an urban water body that receives mainly urban runoff was investigated. Water, suspended solids, and sediment samples were collected during the monsoon (wet) and inter-monsoon (dry) season at different sites and depths. Samples were analyzed for C7 to C12 perfluoroalkyl carboxylate homologues (PFCAs) (PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA), perfluorohexane, perfluorooctane, and 6:2-fluorotelomer sulfonate (PFHxS, PFOS, and 6:2FtS, respectively), perfluorooctane sulfonamide (FOSA), N-ethyl FOSA (sulfluramid), N-ethyl sulfonamidoethanol (N-EtFOSE), and N-methyl and N-ethyl sulfonamidoacetic acid (N-EtFOSAA and N-MeFOSAA, respectively). Concentrations in wet samples were only slightly higher. The sum total PFAS (ΣPFAS) concentrations dissolved in the aqueous phase and sorbed to suspended solids (SS) ranged from 107 to 253 ng/L and 11 to 158 ng/L, respectively. PFOA, PFOS, PFNA, PFHxS, and PFDA contributed most (approximately 90 %) to the dissolved ΣPFASs. N-EtFOSA dominated the particulate PFAS burden in wet samples. K D values of PFOA and PFOS calculated from paired SS and water concentrations varied widely (1.4 to 13.7 and 1.9 to 98.9 for PFOA and PFOS, respectively). Field derived K D was significantly higher than laboratory K D suggesting hydrophobic PFASs sorbed to SS resist desorption. The ΣPFAS concentrations in the top sedimentary layer ranged from 8 to 42 μg/kg and indicated preferential accumulation of the strongly sorbing long-chain PFASs. The occurrence of the metabolites N-MeFOSAA, N-EtFOSAA and FOSA in the water column and sediments may have resulted from biological or photochemical transformations of perfluorooctane sulfonamide precursors while the absence of FOSA, N-EtFOSA and 6:2FtS in sediments was consistent with biotransformation.

Abstract  The structural characterization of polyion complex LB films of perfluoroundecanoic acid-polyethyleneimine was studied using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. From these results, it was found that the fluorocarbon chains in the LB films are located close to the LB film-air interface and are considerably tilted with respect to the surface normal.

Abstract  This study investigated the occurrence of perfluoroalkyl acids (PFAAs) in surface water from 67 sampling sites along rivers of the Pearl River Delta in southern China. Sixteen PFAAs, including perfluoroalkyl carboxylic acids (PFCAs, C5-14, C16 and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8 and C10) were determined by high performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFAA concentrations (∑ PFAAs) in the surface water ranged from 1.53 to 33.5ng·L(-1) with an average of 7.58ng·L(-1). Perfluorobutane sulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonic acid (PFOS) were the three most abundant PFAAs and on average accounted for 28%, 16% and 10% of ∑ PFAAs, respectively. Higher concentrations of ∑ PFAAs were found in the samples collected from Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of extracted sources. Factor 1 (72.48% of the total variance) had high loading for perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), PFBS and PFOS. For factor 2 (10.93% of the total variance), perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUdA) got high loading. The sorption of PFCAs on suspended particulate matter (SPM) increased by approximately 0.1logunits for each additional CF2 moiety and that on sediment was approximately 0.8logunits lower than the SPM logKd values. In addition, the differences in the partition coefficients were influenced by the structure discrepancy of absorbents and influx of fresh river water. These data are essential for modeling the transport and environmental fate of PFAAs.

Abstract  Per- and polyfluoroalkyl substances (PFASs) are used in various industries, which results in their ubiquitous occurrence in the environment. This study determined the concentrations of eighteen PFASs in muscle and liver of nine wild freshwater fish species collected from rivers in the Pearl River Delta (PRD) region, South China, and assessed their bioaccumulation and potential health risks to local people. The results showed that eight and twelve PFASs were detected in the fish muscle and liver samples, respectively. Perfluorooctane sulfonate (PFOS) was found to be the predominant PFAS both in muscle and liver with its highest concentrations of 79ng/g wet weight (ww) in muscle and 1500ng/g ww in liver, followed by Perfluoroundecanoic acid (PFUnDA) and Perfluorotridecanoic acid (PFTrDA) with trace concentrations. The mean PFOS concentrations in fish muscle and liver tissues of the nine collected species ranged from 0.40ng/g in mud carp to 25ng/g in snakehead, and from 5.6ng/g in mud carp to 1100ng/g in snakehead, respectively. Significant positive correlations were found among PFASs both in water and fish, indicating a similar pollution source for these PFASs. In tilapia samples, PFOS concentrations showed an increasing trend with increasing length and weight, but no significant difference between genders. Bioaccumulation factors (logBAF) in fish for the PFASs were in the range from 2.1 to 5.0. The calculated hazard ratios (HR) of PFOS for all fishes were in the range of 0.05-2.8, with four out of nine species (tilapia, chub, leather catfish and snakehead) having their HR values more than 1.0. The results suggest that frequent consumption of these four fish species may pose health risks to local population.

Abstract  Background Charleston Harbor has elevated concentrations of PFAS in dolphins, but local human exposure data are limited. Objectives We sought to describe PFAS serum concentrations’ temporal trends among Gullah African American residents of coastal South Carolina. Methods Longitudinal measures of PFAS in blood serum from a Gullah clinical sample, without lupus, were examined using spaghetti plots and visit-to-visit change scores (e.g., differences in concentrations between visits) among the 68 participants with repeated measures available. We also modeled population-level trends among the 71 participants with any data using proportionate percentile models, accounting for clustering through robust standard errors. In a post-hoc analysis we examined heterogeneity of temporal trends by age through mixed-effects models for the log-transformed PFAS compounds. Results Population concentrations of PFOS dropped approximately 9 (95% CI: 8, 10) percent each year over 2003–2013. This was concordant with individual PFOS trajectories (median PFOS change score −21.7 ng/g wet weight, interquartile range of PFOS change scores: −32.8, −14.9) and reports for other populations over this time period. Several other compounds including PFOA, PFHxS, and PFuNDA also showed a population-level decrease. However, examination of individual trajectories suggested substantial heterogeneity. Post-hoc analyses indicated that PFAS trajectories were heterogeneous by age. Conclusions Many PFAS compounds are decreasing in a sample of Gullah African Americans from coastal South Carolina. There may be age differences in the elimination kinetics of PFASs. The possible role of age as a modifier of PFAS serum trends merits further research.

Abstract  Perfluoroalkyl acids (PFAAs) are a large group of chemicals which are highly persistent in both nature and humans. The use of the most prominent ones, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), was reduced in the early 21st century, and since then levels in human matrices have decreased. However, these two compounds have been exchanged by other PFAAs, for which time trends have not been as extensively investigated. By the use of 80 plasma samples collected between 1987 and 2007 from healthy women (n=1-9 yearly for 1987-2001, n=15 from 2006, and n=10 from 2007), possible time trends of six PFAAs were assessed. Time trends were evaluated for the entire study period, as well as for three sub-periods. As seen in previous studies, levels of perfluorohexane sulfonate (PFHxS), PFOS, and PFOA peaked during the middle time period (1990-2000), with medians of 0.98 ng mL(-1), 18.06 ng mL(-1), and 3.73 ng mL(-1), respectively. However, levels of perfluorononanic acid (PFNA), perfluorodecanic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) increased over the whole study period and most markedly so after year 2000, with medians of 0.73 ng mL(-1), 0.28 ng mL(-1), and 0.24 ng mL(-1), respectively, during the last study period.

Abstract  BACKGROUND, AIM AND SCOPE: Perfluorinated compounds (PFCs) are global environmental pollutants that bioaccumulate in wildlife and humans. Laboratory experiments have revealed toxic effects such as delayed development, humoral suppression, and hepatotoxicity. Although numerous human blood levels have been reported, little is known about distribution in the human body. Knowledge about PFC distribution and accumulation in the human body is crucial to understanding uptake and subsequent effects as well as to conduct risk assessments. The present study reports PFC levels in human liver and breast milk from a general population living in Catalonia, Spain. Liver and milk levels are compared to previously reported levels in blood from the same geographic area as well as to other existing reports on human liver and milk levels in other countries.

MATERIALS AND METHODS: Human liver (n = 12) and milk (n = 10) samples were collected in 2007 and 2008 in Catalonia, Spain. Liver samples were taken postmortem from six males and six females aged 27-79 years. Milk samples were from healthy primipara women (30-39 years old). Both liver and milk were analyzed by solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry.

RESULTS: Six PFCs were detected in liver, with perfluorooctanesulfonate (PFOS, 26.6 ng/g wet weight) being the chemical with the highest mean concentration. Other PFCs such as perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), and acids with chain lengths up to C11 were also detected, with mean levels ranging between 0.50 and 1.45 ng/g wet weight. On the other hand, PFOS and PFHxS were the only PFCs detected in human milk, with mean concentrations of 0.12 and 0.04 ng/mL, respectively.

DISCUSSION: While milk concentrations were similar to reported levels from other countries, liver samples contained more PFCs above quantification limits and higher PFOS concentrations compared to the only two other reports found in the literature. Differences between the results of the present study and those concerning previous investigations can be due to declining levels of some PFCs, which have been reported for the USA. The relationship between PFC concentrations in human liver, milk, and blood was assessed using blood concentrations previously determined in Catalonia. Those levels resulted in liver/serum ratios of 1.7:1, 1.4:1, and 2.1:1 for PFOS, perfluorodecanoic acid, and perfluoroundecanoic acid, respectively. Accumulation in liver is suggested for PFOS and the perfluorocarboxylic acids with carbon chain lengths C9, C10, and C11. For PFOA and PFHxS, fivefold and 14-fold higher concentrations, respectively, were seen in serum as compared to liver. The mean concentration of PFOS and PFHxS in milk was only 0.8% and 0.6% of the reported mean serum level, respectively.

CONCLUSIONS: The results of the present study show that several PFCs could be detected in human liver samples of subjects living in Tarragona. Concerning human milk, the mechanism by which PFCs are transferred from mother's blood to breast milk is still unclear. Considering that PFCs are strongly bound to the protein fraction in blood, the possibility of PFCs entering the milk and accumulating to levels observed in maternal plasma is limited.

RECOMMENDATIONS AND PERSPECTIVES: Interestingly, the potential accumulation difference for PFCs with different chain lengths might be of great importance for risk assessment. Continuing studies on the distribution of different PFCs in human tissue are therefore justified.

Abstract  The concentrations of 10 PFCs (perfluorinated compounds: PFOS, PFHxS, PFOSA, N-EtFOSA, PFDoDA, PFUnDA, PFDA, PFNA, PFOA, and PFHpA) were measured in liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) (n=10) and finless porpoises (Neophocaena phocaenoides) (n=10) stranded in Hong Kong between 2003 and 2007. PFOS was the dominant PFC in the tissues at concentrations ranging at 26-693 ng/g ww in dolphins and 51.3-262 ng/g ww in porpoises. A newly developed combustion ion chromatography for fluorine was applied to measure total fluorine (TF) and extractable organic fluorine (EOF) in these liver samples to understand PFC contamination using the concept of mass balance analysis. Comparisons between the amounts of known PFCs and EOF in the livers showed that a large proportion (approximately 70%) of the organic fluorine in both species is of unknown origin. These investigations are critical for a comprehensive assessment of the risks of these compounds to humans and other receptors.

Abstract  Wastewater treatment plants have recently been identified as a significant pathway for the introduction of perfluoroalkyl surfactants (PASs) to natural waters. In this study, we measured concentrations and fate of several PASs in six wastewater treatment plants (WWTPs) in New York State. We also monitored and measured matrix effects (ionization suppression and enhancement) by postcolumn infusion and standard additions. Concentrations of perfluorooctanoate (PFOA) in effluents of the six WWTPs ranged from 58 to 1050 ng/L. Perfluorooctanesulfonate (PFOS) was also ubiquitous in effluents of these WWTPs, albeit at much lower concentrations (3-68 ng/L). Two of these WWTPs employed identical treatment processes, with similar hydraulic retentions, but differed only in that Plant B treated domestic and commercial waste, whereas Plant A had an additional industrial influence. We found that this industrial influence resulted in significantly greater mass flows of all of the PASs analyzed. Primary treatment was found to have no effect on the mass flows of PASs. Secondary treatment by activated sludge in Plant A significantly increased (p < 0.05) the mass flows of PFOS, PFOA, perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA). However, in Plant B, only the mass flow of PFOA was significantly increased. The observed increase in mass flow of several PASs may have resulted from biodegradation of precursor compounds such as fluorotelomer alcohols, which is supported by significant correlations in the mass flow of PFOA/PFNA and PFDA/PFUnDA. Furthermore, the masses of PFDA and PFUnDA were significantly correlated only after the secondary treatment. In Plant A, concentrations of odd-number PFCAs were greater than those of even-number PFCAs, and concentration decreased with increasing chain length (from C8 to C12). A different pattern was observed in sludge samples, in which the dominance of PFOA decreased, and PFDA and PFUnDA increased, suggesting preferential partitioning of longer-chain PFCAs to sludge.

Abstract  The prevalence and persistence of perfluoroalkyl compounds (PFCs) in environmental and biological systems has been well documented, and a rising number of reports suggest that certain PFCs can result in adverse health effects in mammals. As traditional water sources become increasingly impacted by waste discharge and the demand for planned potable reuse grows, there is recent interest in determining PFC occurrence in drinking water supplies. Here we report monitoring results from drinking water treatment facility samples collected across the United States, and from associated surface, ground, and wastewater sources. Using automated solid phase extraction (SPE) and isotope-dilution liquid chromatography/tandem mass spectrometry (LC/MS-MS), samples were screened for perfluorohexanoic acid (PFHxA), perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA) perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA), and perfluorododecanoic acid (PFDoA). Method reporting limits (MRLs) were established at 1.0 ng/L for all monitored PFCs except PFOA, for which the MRL was set at 5.0 ng/L given elevated procedural and instrumental background levels. PFOS was the only investigated PFC detected in minimally impacted surface waters, with individual site averages of 2.0 ng/L and lower. Conversely, wastewater treatment plant (WWTP) effluents and other highly impacted waters had almost 100% detection frequency for all PFCs except PFUdA and PFDoA, which were not detected above MRL in any samples. Of the investigated PFCs, PFOA averaged the highest overall concentration at any site at 115 ng/L. Substantial impacts from treated wastewater generally caused increased summed PFC concentrations at downstream drinking water facilities, although levels and distribution suggest geographical variability. No discernible differences between influent and effluent PFC levels were observed for drinking water facilities. Removal of PFCs, however, was observed at an indirect potable reuse facility using microfiltration and reverse osmosis for wastewater treatment, in which case all PFC levels in effluents were below the MRL.

Abstract  Perfluorinated alkylated substances (PFAS) have been determined in surface sediments and sediment core from Gulf of Gdańsk, Baltic Sea. Perfluorooctanesulphonate (PFOS), perfluorohexanesulphonate (PFHxS), perfluorodecanoate (PFDA), perfluoronanoate (PFNA), perfluorooctanoate (PFOA), perfluoroheptanoate (PFHpA), perfluoroundecanote (PFUnDA), perfluorododecanoate (PFDoDA) and perfluorohexanoate (PFHxA) were quantified after isotopic dilution ((13)C(4) PFOS and (13)C(4) PFOA), liquid-liquid extractions by methanol and acetonitrile, cleanup by Envi-Carb, OasisWAX and Envi-Carb and final measurement by HPLC-MS/MS. PFOS, PFHxS, PFUnDA, PFDA, PFNA and PFOA were found in Baltic Sea sediments in concentrations exceeding the method limit of quantification (LOQ) of 2 pg/g. PFOS was detected in concentration up to 0.896 ng/g dry weight and PFHxS up to 0.326 ng/g dw, which shows on a weak pollution. PFOS (48-74%) or PFHxS (45-56%) dominated in PFAS composition of sediments surveyed. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Environmental Science and Health, Part A to view the free supplemental file.

Abstract  Long-term temporal trends (1991-2008) and spatial differences of perfluoroalkylated substances (PFASs) were investigated in harbor porpoise (Phocoena phocoena) liver samples of juvenile females from the Baltic and North Sea. Additionally, spatial differences between the populations in the Baltic Sea and Atlantic Ocean (i.e. Iceland and Norway) and the influence of the body mass, age and sex on the PFAS concentrations were examined. Perfluorooctane sulfonate (PFOS) was the predominant compound with a concentration range of 160-2425 ng/g wet weight (ww), followed by perfluorooctane sulfonamide (PFOSA, 1-237 ng/g ww) and perfluoroundecanoate (PFUnA, 3-124 ng/g ww). In terms of temporal trends, perfluoroalkyl sulfonates (PFSAs) and PFOSA concentrations decreased over time, while, conversely, the C(9)-C(13) perfluoroalkyl carboxylate (PFCA) concentrations increased. Spatial distribution of the contaminant concentrations showed consistently higher concentrations in the Baltic Sea and lowest concentrations in the Icelandic population of the Atlantic Ocean.

Abstract  The present study assessed the transactivation potencies of the Baikal seal (Pusa sibirica) peroxisome proliferator-activated receptor α (BS PPARα) by perfluorochemicals (PFCs) having various carbon chain lengths (C4-C12) using an in vitro reporter gene assay. Among the twelve PFCs treated with a range of 7.8-250 μM concentration, eight perfluoroalkyl carboxylates (PFCAs) and two perfluoroalkyl sulfonates (PFSAs) induced BS PPARα-mediated transcriptional activities in a dose-dependent manner. To compare the BS PPARα transactivation potencies of PFCs, the present study estimated the PFOA induction equivalency factors (IEFs), a ratio of the 50% effective concentration of PFOA to the concentration of each compound that can induce the response corresponding to 50% of the maximal response of PFOA. The order of IEFs for the PFCs was as follows: PFOA (IEF: 1)>PFHpA (0.89)>PFNA (0.61)>PFPeA (0.50)>PFHxS (0.41)>PFHxA (0.38)≈PFDA (0.37)>PFBA (0.26)=PFOS (0.26)>PFUnDA (0.15)≫PFDoDA and PFBuS (not activated). The structure-activity relationship analysis showed that PFCAs having more than seven perfluorinated carbons had a negative correlation (r=-1.0, p=0.017) between the number of perfluorinated carbons and the IEF of PFCAs, indicating that the number of perfluorinated carbon of PFCAs is one of the factors determining the transactivation potencies of the BS PPARα. The analysis also indicated that PFCAs were more potent than PFSAs with the same number of perfluorinated carbons. Treatment with a mixture of ten PFCs showed an additive action on the BS PPARα activation. Using IEFs of individual PFCs and hepatic concentrations of PFCs in the liver of wild Baikal seals, the PFOA induction equivalents (IEQs, 5.3-58 ng IEQ/g wet weight) were calculated. The correlation analysis revealed that the hepatic total IEQs showed a significant positive correlation with the hepatic expression levels of cytochrome P450 4A-like protein (r=0.53, p=0.036). This suggests that our approach may be useful for assessing the potential PPARα-mediated biological effects of complex mixtures of PFCs in wild Baikal seal population.

Abstract  Perfluoroalkyl substances (PFASs) have received great attention from the public and scientific community due to their potential adverse impacts on the ecosystem and human health. We investigated the occurrence and distribution of 16 PFASs from 2 classes of PFASs-perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids-in the archived surface sediments of five major rivers (Yellow River, Hai River, Liao River, Zhujiang River, and Dongjiang River) in northern and southern China. The study was also performed during the wet and dry seasons. Perfluorooctanoic acid and perfluorooctane sulfonic acid were the most frequently detected (detection frequency = 100 and 63 %, respectively) in the sediments of the five rivers; the concentrations ranged from 0.08 to 0.99 ng/g dry weight (dw) and were lower than the limit of detection (<LOD), which is 3.89 ng/g dw for both. Perfluorodecanoic acid and perfluoroundecanoic acid were moderately detected (detection frequency = 42 and 44 %, respectively) with concentrations ranging from less than their limit of detection (<LOD) to 0.69 ng/g dw and <LOD to 0.22 ng/g dw, whereas 12 other target analytes were lower than their limit of quantification at most of the sampling sites. Greater concentrations of the PFASs were found at those sites located in urban areas compared with rural areas. Sediment organic content was found to be an important factor influencing the distribution of PFASs in the riverine environment. The results provided first-hand national data of PFASs in the sediments of major rivers in China.

Abstract  Concentrations of perfluorochemicals (PFCs) including perfluoroalkylsulfonates (PFSAs), and perfluoroalkylcarboxylates (PFCAs) were determined in liver of harbor seals (n=68) collected from the northwest Atlantic between 2000 and 2007. Of ten PFCs measured, perfluorooctane sulfonate (PFOS) concentrations were the highest in liver (8-1388 ng/g, ww), followed by perfluoroundecanoic acid (PFUnDA) (<1-30.7 ng/g, ww). An unusual accumulation profile of long-chain (C7-C12) PFCAs, and the predominance of PFUnDA, followed by PFNA in seal liver suggested that fluorotelomer alcohols (FTOHs) may be a major source of PFCAs in the northwest Atlantic. No gender-related differences in the concentrations of individual PFCs or total PFCs were found. Concentrations of PFOS and PFDS were higher in tissues of the pups than the adults, whereas concentrations of the PFCAs were similar between pups and adults. PFOS concentrations in the pups were 2.6-fold higher than those in the adult females, suggesting the importance of maternal transfer of PFCs. Hepatic PFOS concentrations were strongly, positively correlated with PFOSA, PFDS and individual PFCAs, indicating that harbor seals are exposed simultaneously to these compounds. Temporal comparisons of hepatic PFC concentrations showed a marginal increase of PFOS and PFCAs in the adult seals from 2000 to 2007. Unlike the spatial trend observed for polychlorinated biphenyls (PCBs), no south to north (urban-rural-remote) decreasing trend was observed for PFCs, suggesting the presence of diffuse sources of PFC contamination throughout the northwest Atlantic.

Abstract  Perfluoroalkyl substances (PFAS) are persistent and ubiquitous environmental contaminants, and human exposure to these substances may be related to preeclampsia, a common pregnancy complication. Previous studies have found serum concentrations of PFAS to be positively associated with pregnancy-induced hypertension and preeclampsia in a population with high levels of exposure to perfluorooctanoate. Whether this association exists among pregnant women with background levels of PFAS exposure is unknown. Using data from the Norwegian Mother and Child Cohort Study conducted by the Norwegian Institute of Public Health, we carried out a study of nulliparous pregnant women enrolled in 20032007 (466 cases, 510 noncases) to estimate associations between PFAS concentrations and an independently validated diagnosis of preeclampsia. We measured levels of 9 PFAS in maternal plasma extracted midpregnancy; statistical analyses were restricted to 7 PFAS that were quantifiable in more than 50 of samples. In proportional hazards models adjusted for maternal age, prepregnancy body mass index (weight (kg)/height (m)(2)), educational level, and smoking status, we observed no strongly positive associations between PFAS levels and preeclampsia. We found an inverse association between preeclampsia and the highest quartile of perfluoroundecanoic acid concentration relative to the lowest quartile (hazard ratio 0.55, 95 confidence interval: 0.38, 0.81). Overall, our findings do not support an increased risk of preeclampsia among nulliparous Norwegian women with background levels of PFAS exposure.

Abstract  Wildlife from remote locations have been shown to bioaccumulate perfluorinated compounds (PFCs) in their tissues. Twelve PFCs, consisting of perfluorinated carboxylic (PFCA) and sulfonic (PFSA) acids as well as the perfluorooctane sulfonate (PFOS) precursor perfluorooctane sulfonamide (PFOSA), were measured in livers of 68 beluga whales (Delphinapterus leucas) collected from two subpopulations, Cook Inlet and eastern Chukchi Sea, in Alaska between 1989 and 2006. PFOS and PFOSA were the dominant compounds measured in both beluga stock populations, with overall median concentrations of 10.8 ng/g and 22.8 ng/g, respectively. Long-chain perfluorocarboxylates, PFCAs (9 to 14 carbons), were detected in more than 80% of the samples. Perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriA) made up a large percentage of the PFCAs measured with median concentrations of 8.49 ng/g and 4.38 ng/g, respectively. To compare differences in location, year, sex, and length, backward stepwise multiple regression models of the individual and total PFC concentrations were used. Spatially, the Cook Inlet belugas had higher concentrations of most PFCAs and PFOS (p < 0.05); however, these belugas had a lower median concentration of PFOSA when compared to belugas from the eastern Chukchi Sea (p < 0.05). Temporal trends indicated most PFCAs, PFHxS, PFOS, and PFOSA concentrations increased from 1989 to 2006 (p < 0.05). Males had significantly higher concentrations of PFTriA, ΣPFCA, and PFOS (p < 0.05). Perfluorononanic acid (PFNA) and PFOS showed a significant decrease in concentration with increasing animal length (p < 0.05). These observations suggest the accumulation of PFCs in belugas is influenced by year, location, sex, and length.

Abstract  This is the first study to report the concentrations and accumulation profiles of PFCs in marine mammals from Korea. The concentrations and profiles of 10 PFCs in the liver of minke whales and common dolphins from Korean coastal waters were recorded in this study. The mean concentrations of PFOS and PFUnDA were 3-20 times higher than that found for other PFCs analyzed. The concentrations of PFOS in cetaceans from Korea were relatively lower than those reported in other countries. Inter-species differences in the concentrations of PFOS, PFOSA and PFNA were found between two cetacean species, while no difference was observed in the concentrations of PFDA, PFUnDA and PFDoDA between the species. The dominant PFC compounds found in cetaceans were PFUnDA and PFOS, accounting for 70-80% of the PFCs. The accumulation profiles and correlation analysis indicated that two cetacean species have different exposure routes and metabolic capacity for PFCs.

Abstract  Perfluorinated chemicals (PFCs) have been detected in abiotic and biotic matrices worldwide, including the Arctic Ocean. Considering these chemicals' persistent and bioaccumulative potentials, it was expected that levels of PFCs, like those of many legacy organic pollutants, would respond slowly to the restrictions in production and usage. Temporal trend studies in remote areas, such as the Arctic, can help determine the chronology of contamination and the response of the environment to regulations on PFCs. Prior to this study, temporal trends of PFCs in Alaskan coastal waters had not been examined. In the present study, concentrations of six PFCs were determined in livers of northern sea otters (Enhydra lutris kenyoni) collected from three areas in south-central Alaska (Prince William Sound, n = 36; Resurrection Bay, n = 7; Kachemak Bay, n = 34) from 1992 to 2007. Additionally, previously published profiles and concentrations of PFCs in southern sea otters from California and Asian sea otters from Kamchatka (Russia) were compared to our new data, to determine the geographical differences in PFC profiles among these three regions in the Pacific Ocean. Perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (PFOSA), and perfluorononanoate (PFNA) were the predominant PFCs found in the livers of northern sea otters from 1992 to 2007. Other PFCs, such as perfluorooctanoate (PFOA), perfluoroundecanoate (PFUnDA), and perfluorodecanoate (PFDA), were detected less frequently, and at low concentrations. Overall, from 2001 to 2007, a decrease in concentrations of PFOS was found in northern sea otters, suggesting an immediate response to the phase-out in 2000 of perfluorooctanesulfonyl-based compounds by a major producer in the United States. In contrast, concentrations of PFNA in northern sea otters increased by 10-fold from 2004 to 2007. These results indicate that the contribution by PFNA to SigmaPFC concentrations is increasing in northern sea otters. The profiles (i.e., composition of individual PFC to SigmaPFC concentration) of PFCs in northern sea otters from Alaska were similar to those reported for southern sea otters from California, but were considerably different from the profiles reported for Asian sea otters from Russia, suggesting differences in point sources of exposure.

Abstract  Perfluorinated compounds (PFCs) can cross the placental barrier and enter fetal circulation. This study aimed at developing a fast and sensitive ultra-high performance liquid chromatography/tandem mass spectrometry method for the determination of twelve perfluorinated compounds in cord blood. Samples were processed with protein precipitation using formic acid and methanol, mixed with stable isotope labeled standard, followed by sonication and centrifugation, and were analyzed using a Waters ACQUITY UPLC coupled with a Waters Quattro Premier XE triple-quadrupole mass spectrometer. The instrument was operated in selected reaction monitoring (SRM) with negative electrospray ionization. Using BEH C(18) column (2.1 mm×50 mm, 1.7 μm) with 10-mM N-methylmorpholine/methanol gradient elution provided a fast chromatographic separation (5.5 min) and sharp peaks. Intra- and inter-day calibration bias was less than 7% and intra- and inter-day calibration of relative standard deviations were within 0.02-8.22% for all the analytes and concentrations. The recoveries of PFCs spiked into bovine serum ranged from 85 to 104% with relative standard deviations from 0.02 to 6.37%. The limits of quantitation (LOQs), defined as a signal-to-noise ratio of ten, ranged from 0.15 to 3.1 ng/mL for the twelve PFCs. Perfluorooctanoic acid (PFOA), perfluorooctyl sulfonate (PFOS), perfluoroundecanoic acid (PFUA) and perfluorononanoic acid (PFNA) were detected in up to 68% of umbilical cord plasma (n=444) in Taiwan Birth Panel Study and the health effect of these chemicals on children developmental deserves further investigation.

Abstract  Perfluorinated compounds (PFCs) have been used for over 40 years in different commercial and industrial applications mainly as surfactants and surface protectors and have become an important class of marine emerging pollutants. This study presents the development and validation of a new analytical method to determine the simultaneous presence of eight PFCs in different kinds of mollusks using matrix solid-phase dispersion (MSPD) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Simplicity of the analytical procedure, low volume of solvent and quantity of sample required, low global price, and integration of extraction and clean-up into a single step, are the most important advantages of the developed methodology. Solvent, solid support (dispersing agent), clean-up sorbent, and their amounts were optimized by means of an experimental design. In the final method, 0.5 g of sample are dispersed with 0.2 g of diatomaceous earth and transferred into a polypropylene syringe containing 4 g of silica as clean-up sorbent. Then, analytes are eluted with 20 mL of acetonitrile. The extract is finally concentrated to a final volume of 0.5 mL in methanol, avoiding extract dryness in order to prevent evaporation losses and injected in the LC-MS/MS. The combination of this MSPD protocol with LC-MS/MS afforded detection limits from 0.05 to 0.3 ng g(-1). Also, a good linearity was established for the eight PFCs in the range from limit of quantification (LOQ) to 500 ng mL(-1) with R(2) > 0.9917. The recovery of the method was studied with three types of spiked mollusk and was in the 64-126% range. Moreover, a mussel sample was spiked and aged for more than 1 month and analyzed by the developed method and a reference method, ion-pair extraction, for comparison, producing both methods statistically equal concentration values. The method was finally applied to the determination of PFCs in different kinds of mollusks revealing concentrations up to 8.3 ng g(-1) for perfluoroundecanoic acid.