Perfluoroalkyl Sulfonates Research Articles

Organic Anion Transporting Polypeptides Contribute to the Disposition of Perfluoroalkyl Acids in Humans and Rats.

Perfluoroalkyl sulfonates (PFSAs) such as perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) have very long serum elimination half-lives in humans, and preferentially distribute to serum and liver. The enterohepatic circulation of PFHxS and PFOS likely contributes to their extended elimination half-lives. We previously demonstrated that perfluorobutane sulfonate (PFBS), PFHxS, and PFOS are transported into hepatocytes both in a sodium-dependent and a sodium-independent manner. We identified Na+/taurocholate cotransporting polypeptide (NTCP) as the responsible sodium-dependent transporter. Furthermore, we demonstrated that the human apical sodium-dependent bile salt transporter (ASBT) contributes to the intestinal reabsorption of PFOS. However, so far no sodium-independent uptake transporters for PFSAs have been identified in human hepatocytes or enterocytes. In addition, perfluoroalkyl carboxylates (PFCAs) with 8 and 9 carbons were shown to preferentially distribute to the liver of rodents; however, no rat or human liver uptake transporters are known to transport these PFCAs. Therefore, we tested whether PFBS, PFHxS, PFOS, and PFCAs with 7-10 carbons are substrates of organic anion transporting polypeptides (OATPs). We used CHO and HEK293 cells to demonstrate that human OATP1B1, OATP1B3, and OATP2B1 can transport PFBS, PFHxS, PFOS, and the 2 PFCAs (C8 and C9). In addition, we show that rat OATP1A1, OATP1A5, OATP1B2, and OATP2B1 transport all 3 PFSAs. In conclusion, our results suggest that besides NTCP and ASBT, OATPs also are capable of contributing to the enterohepatic circulation and extended human serum elimination half-lives of the tested perfluoroalkyl acids.

Distribution of perfluoroalkyl compounds in Osaka Bay and coastal waters of Western Japan

Perfluoroalkyl acids (PFAAs) including perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) were analyzed in sediment samples taken from Ajifu Waterway in Osaka city, from Osaka Bay, and from Kagoshima Bay, as well as in fifteen seawater samples collected from Osaka Bay and coastal waters of Western Japan. In all sediment samples, only PFCAs were detected, and the highest concentration was determined in Ajifu Waterway, where ΣPFAA was 58990 ng kg−1 dry weight. The total concentrations of PFAAs in sea water samples ranged between the limit of quantification and 53.4 ng L−1, and perfluorohexanoic acid was the most prevalent and had the highest concentration of 37 ng L−1. The changes in the patterns and concentrations of PFAAs in Osaka Bay and coastal waters of Western Japan indicate that the PFAAs in surface waters are influenced by sources from Keihanshin Metropolitan Area, mainly the Yodo River basin, and the dilution effect which naturally occurs during their transport to the Pacific Ocean.

Perfluorinated alkyl substances (PFASs) in northern Spain municipal solid waste landfill leachates

Landfill leachates have been recognized as significant secondary sources of poly- and perfluoroalkyl substances (PFASs). This study presents data on the occurrence and concentration of 11 perfluoroalkyl carboxylates (PFCAs) and 5 perfluoroalkyl sulfonates (PFSAs) in leachates from 4 municipal solid waste landfill sites located across northern Spain. To the best of our knowledge, this is the first report of the presence of PFASs in Spanish landfill leachates. Two of the landfill sites applied on-site treatment using membrane bioreactors (MBR), and its effect on PFASs occurrence is also reported. Total PFASs (∑PFASs) in raw leachates reached 1378.9 ng/L, while in treated samples ∑PFASs was approximately two-fold (3162.3 ng/L). PFCAs accounted for the majority of the detected PFASs and perfluorooctanoic acid (PFOA) was the dominant compound in raw leachates (42.6%), followed by shorter chain PFHxA (30.1%), PFPeA and PFBA. The age of the sites might explain the PFASs pattern found in raw leachates as all of them were stabilized leachates. However, PFASs profile was different in treated samples where the most abundant compound was PFHxA (26.5%), followed by linear perfluorobutane sulfonate (L-PFBS) (18.7%) and PFOA (17.7%). The overall increase of the PFASs content as well as the change in the PFASs profile after the MBR treatment, could be explained by the possible degradation of PFASs precursors such as fluorotelomer alcohols or fluorotelomer sulfonates. Using the volume of leachates generated in the landfill sites, that served 1.8 million people, the discharge of 16 ∑PFASs contained in the landfill leachates was estimated as 1209 g/year.

Endocrine-disruption potential of perfluoroethylcyclohexane sulfonate (PFECHS) in chronically exposed Daphnia magna

Perfluoroethylcyclohexane sulfonate (PFECHS), mainly used in hydraulic fluids in aircrafts, is a member of the perfluoroalkyl sulfonate family which includes the regulated perfluorooctane sulfonate (PFOS). PFECHS has been reported in environmental samples but its toxicity to aquatic organisms is unknown. The objectives of this study were to identify biological pathways altered by sublethal exposure (12 d) of D. magna to PFECHS (0.06, 0.6, and 6 mg/L) using microarray and quantitative real-time PCR and to identify potential biomarkers to link transcriptomic to phenotypic responses. PFECHS was also quantified in surface water samples (1.04–1.38 ng/L) collected from the St. Lawrence River, Canada. Transcriptomic analyses indicated the under-regulation of vitellogenin-related genes (VTG1) in PFECHS-exposed groups. PFECHS exposure also led to the up-regulation of genes related to cuticle. VTG was selected as a potential cellular marker and identified in D. magna using an immuno-specific assay and quantified using Western blot and LC/MS/MS. Results indicated a decrease of VTG content in exposed D. magna which was in concordance with the transcription of VTG-related genes. No effects were observed on survival, molting, or reproduction at the individual/population levels. Overall, results suggest endocrine disruption potential for PFECHS in D. magna at concentrations higher than levels reported in the aquatic environment.

Distribution of perfluorinated alkylated substances (PFAS) in blood compartments during prenatal exposure

-Introduction: Perfluorinated compounds (PFASs) are a class of persistent environmental toxicants widely used due to their unique chemical and physical properties. Knowledge on the health effects in humans is sparse and have most often been studied for PFOA and PFOS. Knowledge of prenatal exposure, and distribution between blood compartments for a wider range of PFASs in humans is therefore needed. -Methods: We present prenatal exposure data for 19 perfluorinated organic compounds from 101 mother and child pairs. The compounds were quantified in maternal serum as well as in umbilical cord whole blood and in serum from the child at birth. The samples were collected between 1999-2001 at the Faroe Islands. The quantified compounds includes the two major subgroups perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFSAs) ranging from C4-C12, as well as perfluorooctanesulfonamides (FOSAs) and perfluorooctanesulfonamidoacetic acids (FOSAAs). -Results: The PFAS concentration in maternal and the foetal samples were significantly correlated for nearly all PFASs with median concentrations in cord serum ranging between 30-95% of the maternal concentration. The cord whole blood and cord serum concentrations were also significantly correlated, although the concentration in the whole blood were lower. The only exception was FOSA that binds to erythrocytes and therefore occur at significantly higher concentration in whole blood. The apparent partition of the PFCs across the placental barrier varied according to chain length, branching and active group. Increasing chain length was associated with decreased passage. Branched PFOS were comparatively higher on the foetal side than linear PFOS, and the carboxylates seemed to pass more easily than sulfonates for compounds at the same length. -Conclusion: The concentration of PFASs is significantly correlated between the mother and the child, as well as in the cord whole blood and serum compartments in the child.

Occurrence and distribution of perfluoroalkyl acids (PFAAs) in surface water and sediment of a tropical coastal area (Bay of Bengal coast, Bangladesh)

This study reports the first evidence of perfluoroalkyl acids (PFAAs) in surface waters and sediments collected from the coastal area of Bangladesh. Fifteen target PFAAs, including C4–14-PFCAs (perfluoroalkyl carboxylates) and C4, C6, C8, and C10-PFSAs (perfluoroalkyl sulfonates), were quantified by HPLC–MS/MS. The ΣPFAAs in surface water and sediment samples were in the range of 10.6 to 46.8ng/L and 1.07 to 8.15ng/gdw, respectively. PFOA in water (3.17–27.8ng/L) and PFOS in sediment samples (0.60–1.14ng/gdw) were found to be the most abundant PFAAs, and these concentrations were comparable to or less than most other reported values, particularly those recorded from the coastal areas of China, Japan, Korea and Spain. The majority of the monitored PFAAs did not show clear seasonal variation. The southeastern part (Cox’s Bazar and Chittagong) of the Bangladeshi coastal area was more contaminated with PFAAs than the southern (Meghna Estuary) and southwestern parts (Sundarbans). Industrial and municipal wastewater effluents, ship breaking and port activities were identified as potential sources of the PFAA contamination in this region. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced the variability between samples. The values of log KD (1.63–2.88) and log KOC (4.02–5.16) were higher than previously reported values, which may indicate that the partitioning of PFAAs in a tropical coastal ecosystem is different from other ecosystems, such as temperate and sub-tropical regions. Although a preliminary environmental hazard assessment indicated that PFOA or PFOS levels do not currently exceed the acute safety thresholds, we should keep in mind that they are bioavailable and can accumulate in the food chain. Therefore, the ubiquity of PFAAs in the coastal area of Bangladesh warrants further studies characterizing their specific sources and the potential long-term risks they present to both humans and wildlife.

The perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonates (PFSAs) contamination level in spices

Spices have been used since ancient times. Although they have been employed mainly as flavoring and coloring agents, their role in food safety is of increasing concern. In this study, the usefulness of a modified QuEChERS method, based on the d-SPE, with micro-HPLC–MS/MS system for the determination of selected perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonates (PFSAs) in spices was addressed. The commonly used spices in Spain and Slovakia were investigated. The studies showed the presence of perfluorooctanoic acid in 19 spices of Spanish and Slovak origin, and it ranged from 0.11 ng g−1 for garlic to 0.67 ng g−1 for peppermint. The perfluorobutanoic acid was quantified in 10 Slovak spices (from 1.13 ng g−1 for allspice to 37.82 ng g−1 for star anise), whereas perfluorobutane sulfonate was identified only in 12 Spanish spices and it ranged from 0.24 ng g−1 for cinnamon to 1.01 ng g−1 for coriander. In contrast, perfluoroheptanoic acid was identified only in Slovak cardamom (1.94 ng g−1) and coriander (0.74 ng g−1). The average consumption of spices in Europe is approximately 0.5 g day−1, while in Asia and northern Africa, it is many times higher. Average content of PFASs in this evaluation has a value 4.67 ng g−1 giving 2.33 ng day−1 per person. This study showed that daily used spices may contribute to the overall contamination of food by perfluoroalkyl substances.

Isomer-Specific Distribution of Perfluoroalkyl Substances in Blood.

Perfluoroalkyl substances (PFASs) such as perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and PFOS-precursors are routinely measured in human plasma and serum, but their relative abundance in the blood cell fraction has not been carefully examined, particularly at the isomer-specific level. Human plasma and whole blood were collected and partitioning behaviors of PFASs and their isomers between plasma and blood cells were investigated. In human samples, mass fraction in plasma (Fp) for PFASs increased among perfluoroalkyl carboxylates as the carbon chain length increased from C6 (mean 0.24) to C11 (0.87), indicating preference for the plasma fraction with increasing chain length. However, among perfluoroalkyl sulfonates, PFHxS (mean 0.87) had a slightly higher Fp than PFOS (0.85). In vitro assays with spiked Sprague-Dawley rat blood were also conducted, and the results showed that PFOS-precursors had lower Fp values than perfluoroalkyl acids, with perfluoroctanesulfonamide having the lowest Fp (mean 0.24). Consistently, linear isomers of PFOS and PFOS-precursors had lower mean Fp than their corresponding total branched isomers. Multiplying by a factor of 2 is not a reasonable method to convert from whole blood to plasma PFAS concentrations, and current ratios could be used as more accurate conversion factors.

Elevated levels of short carbon-chain PFCAs in breast milk among Korean women: Current status and potential challenges

Breast milks can be contaminated with perfluoroalkyl substances (PFASs). Exposure to PFASs during early stages of life may lead to adverse health effects among breastfed infants. To date, perfluorootanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been most frequently measured PFASs in breast milks worldwide. Information on shorter carbon-chain PFASs in breast milk is scarce. In this study, breast milks were sampled from 264 Korean lactating women, and measured for seventeen PFASs, including ten perfluoroalkyl carboxylates (PFCAs), four perfluoroalkyl sulfonates, and three perfluoroalkyl sulfonamides. PFOA and PFOS were detected in 98.5% of the breast milk samples, with median concentrations of 0.072 and 0.050ng/mL, respectively. Perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), and perfluoroheptanoic acid (PFHpA) were detected in higher frequencies, ranging between 67.4% and 81.8%. The concentrations of short carbon-chain PFCAs in breast milk such as PFPeA and PFHxA were the highest ever reported to date, and were comparable to that of PFOS. Concentrations of shorter chain PFCA in breast milk tended to be higher among the women with longer lactation period, while those of PFOA showed the opposite trend, suggesting a possibility that breastfeeding might be an important route of excretion for PFOA among lactating women. Fish consumption and the use of consumer products, e.g., skin care products, cosmetics and non-stick coated cooking utensils, were identified as significant predictors of PFAS concentrations in breast milk. Health risks associated with PFOA and PFOS exposure through breastfeeding were estimated negligible, however, risks of the short carbon-chain PFCAs could not be assessed because of lack of relevant toxicological information. Further efforts for source identification and exposure management measures for shorter chain PFCAs are necessary.

Spatial and temporal trends in perfluoroalkyl substances (PFASs) in ringed seals (Pusa hispida) from Svalbard

This study investigates concentrations of perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFSAs) and perfluoroalkane sulfonamides (FASA) in plasma from ringed seals sampled in the period 1990–2010 (n = 71) in Svalbard, Norway. Perfluorooctane sulfonate was dominant among the perfluoroalkyl substances. PFCAs were dominated by perfluoroundecanoate followed by perfluorononanoate. C4C8 PFCAs and perfluorooctane sulfonamide (FOSA) were detected in ≤42% of the samples. PFSA and PFCA concentrations were higher in seals sampled from Kongsfjorden, a fjord influenced by strong inflows of Atlantic Water compared to seals from fjords dominated by Arctic Water (e.g. Billefjorden). Sex, age and body condition of the seals did not influence PFAS concentrations. Due to the confounding effect of year and sampling area, temporal trends were assessed only in seals sampled from Kongsfjorden (5 years, n = 51). PFHxS and PFOS concentrations did not show significant linear trends during the whole study period, but a decrease was observed since 2004. Concentrations of all of the detected PFCAs (C9C13 PFCAs) increased until 2004 after which they have declined or stabilized.

Annual dynamics of perfluorinated compounds in sediment: A case study in the Morava River in Zlín district, Czech Republic

Two groups of perfluorined compounds (PFCs), i.e. perfluoroalkyl sulfonates (PFASs) and perfluoroalkyl carboxylates (PFCAs) were analysed during a period of 1 year in monthly collected riverbed sediment samples from five sampling sites in an industrial region in Morava River catchment in Czech Republic. Levels of PFCs determined in sediment samples were up to 6.8 μg kg−1 of dry weight. Among PFCs analysed, mainly short-chain PFASs (C6 to C8) including PFOS were found in sediment samples and their levels were similar to those found in comparable river basins in other parts of Europe. Concentrations of PFCs were correlated with organic carbon content and their variations were mainly correlated by high flow events on Morava River and its tributaries. The changes in PFC concentrations were induced by displacing of PFCs containing particles to the river sediment during these elevated flow events.

Fast and simple determination of perfluorinated compounds and their potential precursors in different packaging materials

A simple and fast analytical method for the determination of fourteen perfluorinated compounds (PFCs), including three perfluoroalkylsulfonates (PFSAs), seven perfluorocarboxylic acids (PFCAs), three perfluorophosphonic acids (PFPAs) and perfluorooctanesulfonamide (PFOSA) and ten potential precursors, including four polyfluoroalkyl phosphates (PAPs), four fluorotelomer saturated acids (FTCAs) and two fluorotelomer unsaturated acids (FTUCAs) in different packaging materials was developed in the present work. In order to achieve this objective the optimization of an ultrasonic probe-assisted extraction (UPAE) method was carried out before the analysis of the target compounds by liquid-chromatography-triple quadrupole-tandem mass spectrometry (LC-QqQ-MS/MS). 7mL of 1 % acetic acid in methanol and a 2.5-min single extraction cycle were sufficient for the extraction of all the target analytes. The optimized analytical method was validated in terms of recovery, precision and method detection limits (MDLs). Apparent recovery values after correction with the corresponding labeled standard were in the 69–103 % and 62–98 % range for samples fortified at 25ng/g and 50ng/g concentration levels, respectively and MDL values in the 0.6–2.2ng/g range were obtained. The developed method was applied to the analysis of plastic (milk bottle, muffin cup, pre-cooked food wrapper and cup of coffee) and cardboard materials (microwave popcorn bag, greaseproof paper for French fries, cardboard box for pizza and cinema cardboard box for popcorn). To the best of our knowledge, this is the first method that describes the determination of fourteen PFCs and ten potential precursors in packaging materials. Moreover, 6:2 FTCA, 6:2 FTUCA and 5:3 FTCA analytes were detected for the first time in microwave popcorn bags.

Simultaneous qualitative and quantitative analysis of fluoroalkyl sulfonates in riverine water by liquid chromatography coupled with Orbitrap high resolution mass spectrometry

In this study, a robust method for quick screening, confirmation and quantification analysis of eight fluoroalkyl sulfonates in surface riverine samples was developed using ultra-high performance liquid chromatography-high resolution mass spectrometer (LC-Orbitrap Tribrid HRMS). Weak anion exchange solid phase extraction was optimized to maximum recover perfluoroalkyl sulfonates (PFSAs), fluorotelomer sulfonates and the emerging 6:2 chlorinated polyfluoroalkyl ether sulfonate at the same time. Both qualitative and quantitative purposes could be achieved by simultaneous acquiring full-scan mass spectrum (MS1) and data-dependent MS2 data. The LC-Orbitrap Tribrid HRMS method showed competent method detection limits for all analytes (7.1–62pg/L) compared with the triple quadrupole mass spectrometry (LC–MS/MS) quantification method (12–54pg/L), and satisfactory method validation results were also obtained in linearity (R2>0.999), trueness (88–118%), precision (2–17%) and recovery (63–103%). A good correlation (R>0.999) was found between the sets of quantified PFSA residue concentrations in thirteen estuary river samples by both the LC-Orbitrap Tribrid HRMS (0.2–440ng/L) and LC–MS/MS (0.1–424ng/L) methods, indicating that Orbitrap Tribrid HRMS could be used for reliable quantitative analysis purpose. Moreover, the LC-Orbitrap Tribrid HRMS method could also benefit from its high mass resolution characteristic to eliminate potential environment interferents (e.g., taurodeoxycholate) and to quantify all PFSA isomers based on full-scan MS1 chromatogram at a narrow MS window (5 part per million).

Microbial toxicity and biodegradability of perfluorooctane sulfonate (PFOS) and shorter chain perfluoroalkyl and polyfluoroalkyl substances (PFASs).

Perfluorooctane sulfonate (PFOS) and related perfluoroalkyl and polyfluoroalkyl substances (PFASs) are emerging contaminants that have been widely applied in consumer and industrial applications for decades. However, PFOS has raised public concern due to its high bioaccumulative character, environmental persistence, and toxicity. Shorter PFASs such as perfluorobutane sulfonate (PFBS) and polyfluoroalkyl compounds have been proposed as alternatives to PFOS but it is unclear whether these fluorinated substances pose a risk for public health and the environment. The objective of this research was to investigate the microbial toxicity and the susceptibility to microbial degradation of PFOS and several related fluorinated compounds, i.e., short-chain perfluoroalkyl and polyfluoroalkyl sulfonic and carboxylic acids. None of the compounds tested were toxic to the methanogenic activity of anaerobic wastewater sludge even at very high concentrations (up to 500 mg L-1). All PFASs evaluated were highly resistant to microbial degradation. PFOS was not reductively dehalogenated by the anaerobic microbial consortium even after very long periods of incubation (3.4 years). Similarly, the tested short chain perfluoroalkyl substances (i.e., PFBS and trifluoroacetic acid) and a polyfluoroalkyl PFOS analogue, 6 : 2 fluorotelomer sulfonic acid (FTSA) were also resistant to anaerobic biodegradation. Likewise, no conclusive evidence of microbial degradation was observed under aerobic conditions for any of the short-chain perfluoroalkyl and polyfluoroalkyl carboxylic acids tested after 32 weeks of incubation. Collectively, these results indicate that PFOS and its alternatives such as short chain perfluoroalkyl sulfonates and carboxylates and their polyfluorinated homologues are highly resistant to microbial degradation.

Perfluoroalkyl sulfonates and carboxylic acids in liver, muscle and adipose tissues of black-footed albatross (Phoebastria nigripes) from Midway Island, North Pacific Ocean

The Great Pacific Garbage Patch (GPGP) is a gyre of marine plastic debris in the North Pacific Ocean, and nearby is Midway Atoll which is a focal point for ecological damage. This study investigated 13 C4–C16 perfluorinated carboxylic acids (PFCAs), four (C4, C6, C8 and C10) perfluorinated sulfonates and perfluoro-4-ethylcyclohexane sulfonate [collectively perfluoroalkyl acids (PFAAs)] in black-footed albatross tissues (collected in 2011) from Midway Atoll. Of the 18 PFCAs and PFSAs monitored, most were detectable in the liver, muscle and adipose tissues. The concentrations of PFCAs and PFSAs were higher than those in most seabirds from the arctic environment, but lower than those in most of fish-eating water birds collected in the U.S. mainland. The concentrations of the PFAAs in the albatross livers were 7-fold higher than those in Laysan albatross liver samples from the same location reported in 1994. The concentration ranges of PFOS were 22.91–70.48, 3.01–6.59 and 0.53–8.35ngg−1 wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04–18.70ngg−1 ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and PFODA were below limit of quantification. C8–C13 PFCAs showed much higher composition compared to those found in other wildlife where PFOS typically predominated. The concentrations of PFUdA in all 8 individual albatross muscle samples were even higher than those of PFOS. This phenomenon may be attributable to GPGP as a pollution source as well as PFAA physicochemical properties.

Na+/Taurocholate Cotransporting Polypeptide and Apical Sodium-Dependent Bile Acid Transporter Are Involved in the Disposition of Perfluoroalkyl Sulfonates in Humans and Rats.

Among the perfluoroalkyl sulfonates (PFASs), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) have half-lives of several years in humans, mainly due to slow renal clearance and potential hepatic accumulation. Both compounds undergo enterohepatic circulation. To determine whether transporters involved in the enterohepatic circulation of bile acids are also involved in the disposition of PFASs, uptake of perfluorobutane sulfonate (PFBS), PFHxS, and PFOS was measured using freshly isolated human and rat hepatocytes in the absence or presence of sodium. The results demonstrated sodium-dependent uptake for all 3 PFASs. Given that the Na(+)/taurocholate cotransporting polypeptide (NTCP) and the apical sodium-dependent bile salt transporter (ASBT) are essential for the enterohepatic circulation of bile acids, transport of PFASs was investigated in stable CHO Flp-In cells for human NTCP or HEK293 cells transiently expressing rat NTCP, human ASBT, and rat ASBT. The results demonstrated that both human and rat NTCP can transport PFBS, PFHxS, and PFOS. Kinetics with human NTCP revealed Km values of 39.6, 112, and 130 µM for PFBS, PFHxS, and PFOS, respectively. For rat NTCP Km values were 76.2 and 294 µM for PFBS and PFHxS, respectively. Only PFOS was transported by human ASBT whereas rat ASBT did not transport any of the tested PFASs. Human OSTα/β was also able to transport all 3 PFASs. In conclusion, these results suggest that the long half-live and the hepatic accumulation of PFOS in humans are at least, in part, due to transport by NTCP and ASBT.

Identification of Novel Polyfluorinated Ether Sulfonates as PFOS Alternatives in Municipal Sewage Sludge in China.

A 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFAES) with the trade name F-53B, is an alternative to perfluorooctanesulfonate (PFOS) in electroplating industry that is uniquely used in China. It was developed as a mist suppressant initially in the 1970s, but the environmental behaviors and potential adverse effects of the 6:2 Cl-PFAES have only recently been investigated. In this work, the occurrence and distribution of perfluoroalkyl sulfonate (PFSA), fluorotelomer sulfonate (FTSA), and PFAES analogues were investigated in municipal sewage sludge samples collected around China. Perfluorobutane, perfluorohexane, perfluorooctane, and perfluorodecanesulfonates, 6:2 and 8:2 FTSAs, and the emerging 6:2 Cl-PFAES were detected. Moreover, 8:2 and 10:2 Cl-PFAESs were identified for the first time as new polyfluorinated contaminants using high resolution mass spectrometry. These fluorinated analytes were further quantified with the aid of commercial and laboratory-purified standards. PFOS was the predominant contaminant with a geometric mean (GM) value of 3.19 ng/g dry weight (d.w.), which was subsequently followed by 6:2 Cl-PFAES and 8:2 Cl-PFAES (GM: 2.15 and 0.50 ng/g d.w., respectively). Both 6:2 and 8:2 Cl-PFAES were positively detected as the major components in the F-53B commercial product, and discrete 6:2 Cl-PFAES/8:2 Cl-PFAES ratios in the product and sludge samples might suggest 8:2 Cl-PFAES had enhanced sorption behavior in the sludge due to the increase in hydrophobicity.

Temporal trends of perfluoroalkyl substances (PFAS) in eggs of coastal and offshore birds: Increasing PFAS levels associated with offshore bird species breeding on the Pacific coast of Canada and wintering near Asia.

Perfluoroalkyl substances (PFAS) such as perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) have become virtually ubiquitous throughout the environment, and, based on laboratory studies, have known toxicological consequences. Various national and international voluntary phase-outs and restrictions on these compounds have been implemented over the last 10 to 15 years. In the present study, we examine trends (1990/1991-2010/2011) in aquatic birds (ancient murrelet, Synthliboramphus antiquus [2009 only]; Leach's storm-petrels, Oceanodroma leucorhoa; rhinoceros auklets, Cerorhinca monocerata; double-crested cormorants, Phalacrocorax auritus; and great blue herons, Ardea herodias). The PFCA, PFSA, and stable isotope (δ(15) N and δ(13) C) data collected from these species from the Pacific coast of Canada, ranging over 20 to 30 years, were used to investigate temporal changes in PFAS coupled to dietary changes. Perfluorooctane sulfonic acid (PFOS), the dominant PFSA compound in all 4 species, increased and subsequently decreased in auklet and cormorant eggs in line with the manufacturing phase-out of PFOS and perfluorooctanoic acid (PFOA), but concentrations continuously increased in petrel eggs and remained largely unchanged in heron eggs. Dominant PFCA compounds varied between the offshore and coastal species, with increases seen in the offshore species and little or variable changes seen in the coastal species. Little temporal change was seen in stable isotope values, indicating that diet alone is not driving observed PFAS concentrations.

Isomer profiles of perfluoroalkyl substances in water and soil surrounding a chinese fluorochemical manufacturing park.

Despite that China is the largest global manufacturer of perfluoroalkyl substances (PFASs), the manufacturing methods and isomer purity of these chemicals are generally unknown. Here, sampling was conducted around a major fluorochemical manufacturing park in China in 2012, including soil and water collection inside the park, including from a wastewater treatment plant (WWTP), as well as in surrounding rivers and soil (∼15 km radius). Perfluoroalkyl sulfonates (PFSAs) were lower than perfluoroalkyl carboxylates (PFCAs) in all samples, and short-chain (C4-C6) PFCAs were predominant. Perfluoroalkyl phosphonates and phosphate diesters were occasionally detected, but at low detection frequency. Branched isomers of perfluorobutanesulfonate (PFBS) are reported for the first time, accounting for 15-27% of total PFBS in water. An enrichment of isopropyl-PFOA (28%) was found in WWTP influent, suggesting its manufacturing primarily by isopropyl telomerization. More numerous branched isomers were observed for the longer C9-C13 PFCAs (e.g., C12 PFCA had 16 branched isomers), including high proportions of one major branched isomer (likely isopropyl), possibly as impurities from isopropyl-PFOA manufacturing. Overall, short-chain perfluorinated acids were the predominant PFASs being released, but PFOA was still a major chemical in use at this site, primarily from isopropyl telomerization.

Discovery and Implications of C2 and C3 Perfluoroalkyl Sulfonates in Aqueous Film-Forming Foams and Groundwater

Historically, 3M aqueous film-forming foams (AFFFs) were released at U.S. military and civilian sites to extinguish hydrocarbon-based fuel fires. To date, only C4–C10 homologues of the perfluoroalkyl sulfonic acids (PFSAs) are documented in 3M AFFFs. Perfluoroethanesulfonate (PFEtS) and perfluoropropanesulfonate (PFPrS), two ultra-short-chain PFSAs, were discovered by liquid chromatography (LC) quadrupole time-of-flight mass spectrometry. Once they were identified, PFEtS and PFPrS were then quantified in five 3M AFFFs and in one groundwater sample from each of 11 U.S. military bases by LC tandem mass spectrometry. Concentrations of PFEtS and PFPrS in the five AFFFs ranged from 7 to 13 mg/L and from 120 to 270 mg/L, respectively. For the groundwater, PFEtS was quantified in 8 of the 11 samples (11–7500 ng/L) and PFPrS in all samples (19–63000 ng/L). The high water solubility, mobility, and detection frequency of these ultra-short-chain PFSAs indicate that groundwater contaminant plumes may be larger than p...