Abstract  A laboratory investigation on the biotransformation of 8:2 fluorotelomer stearate monoester (8:2 FTS) in aerobic soils was conducted by monitoring the loss of 8:2 FTS, production of 8:2 fluorotelomer alcohol (8:2 FTOH) and stearic acid, which would be released by cleavage of the ester linkage, and subsequent degradation products from FTOH for 80 d. Soil microcosms were extracted with ethyl acetate followed by two heated 90/10 v/v acetonitrile/200 mM NaOH extractions. 8:2 FTS was degraded with an observed half-life (t(1/2)) of 10.3 d. The rate of 8:2 FTS biotransformation substantially decreased after 20 d with 22% of 8:2 FTS still remaining on day 80. No biotransformation of 8:2 FTS occurred in autoclaved soil controls, which remained sterile with 102 ± 6% recovery, through day 20. 8:2 FTOH was generated with cleavage of the ester linkage of 8:2 FTS followed by a rapid decline (t(1/2) ~ 2 d) due to subsequent biodegradation. All the expected 8:2 FTOH degradation products were detected including 8:2 fluorotelomer unsaturated and saturated carboxylic acids, 7:2s FTOH, 7:3 acid, and three perfluoroalkyl carboxylic acids with the most prominent being perfluorooctanoic acid (PFOA). PFOA consistently increased over time reaching 1.7 ± 0.07 mol % by day 80. Although cleavage of the ester linkage was evidenced by 8:2 FTOH production, an associated trend in stearic acid concentrations was not clear because of complex fatty acid metabolism dynamics in soil. Further analysis of mass spectrometry fragmentation patterns and chromatography supported the conclusion that hydrolysis of the ester linkage is predominantly the first step in the degradation of 8:2 FTS with the ultimate formation of terminal products such as PFOA.

Abstract  Although industrial sites producing perfluoroalkyl and polyfluoroalkyl substances (PFASs) may introduce these chemicals into the aquatic environment, they are rarely investigated. This study entailed measuring concentrations, mass flows and the fate of 51 PFASs in an industrial wastewater treatment plant receiving raw effluents from a fluorochemical manufacturing facility. Grab and 24-h composite samples were collected at various stages of wastewater treatment over four sampling campaigns. One perfluoroalkyl carboxylic acid (PFCA) and nine fluorotelomers (FTs) were systematically detected in the facility's raw effluent. The overall PFCA mass flow ranged from 0.6 to 8.6g/day and was negligible compared to the overall mass flow of FTs (from 647 to 2,892g/day). PFCA mass flows increased drastically after secondary treatment (degradation of precursors) and decreased notably after the floatation tank (adsorption onto floatation sludge), but remained at relatively high levels in the final effluent (from 21 to 247g/day). Similar patterns in mass flow were observed for the FTs, with mass loadings discharged into the river ranging from 1,623 to 6,963g/day. Despite analyzing dozens of PFASs, adsorbable organic fluorine determination and oxidative conversion of PFCA precursors showed that a significant part of PFASs remained unidentified. Nevertheless, two overwhelmingly predominant PFASs-6:2 Fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) and 6:2 Fluorotelomer sulfonamide propyl N,N dimethylamine (M4)-were detected and quantified for the first time in water samples, accounting for >75% of the total PFAS mass flow in the final effluent. This study also provided evidence of soil contamination by the aerosol produced over the aeration basin and inadvertent spillage of pieces of sludge cake.

Abstract  Supplemental materials

Abstract  OBJECTIVE: To develop a method for the determination of 11 perfluorosulfonate and perfluorocarboxylate precursors in eggs using ultra-high performance liquid chromatography-tandem quadruple mass spectrometry (UPLC-MS/MS).

METHODS: The target compounds of egg were extracted with 100 mmol/L NaOH-acetonitrile /water(90∶10, V/V) by ultrasonic. Then the extract was purified by solid phase extraction (Waters Oasis(@) WAX 6cc) and then eluted with 9% NH4OH in methanol. The target compounds were separated on a Waters ACQUITY(TM) BEH (18)C column (50 mm × 2.1 mm, 1.7 μm) and detected by negative electrospray ionization (ESI(-)) mass spectrometry in multiple reaction monitoring mode (MRM). All compounds were quantified with internal standards. The accuracy, precision and the limits of detection and quantification of the method were evaluated. Then we detected 7 different egg samples from the market.

RESULTS: The average recoveries for the eleven precursors at 3 levels were 74.09%-116.82% and the relative standard deviations were 2.37%-13.62%. The limits of detection (LOD) of the method were in the range of 0.06-1.50 pg/g (wet weight) and the limits of quantification (LOQ) were in the range of 0.15-3.00 pg/g (wet weight). And 5 target compounds were detected in the 7 market samples. 6:2 fluorotelomer sulfonate (6:2 FTS) was detected in all of samples with the concentrations of 1.67-3.11 pg/g. 6:2 fluorotelomer unsaturated acid (FHUEA) and 6:2 disubstituted polyfluoroalkyl phosphate ester (6:2 diPAP) were detected in 6 samples and the concentrations were<LOD-5.11 pg/g and 3.78-9.16 pg/g, respectively. And the concentrations of 8:2 fluorotelomer sulfonate (8:2 FTS) and N-methyl perfluorooctane sulfonamidoacetic acid (N-Me FOSAA) founded in the same sample were 105.78, and 4.95 pg/g, respectively.

CONCLUSION: This method was simple, rapid, and suitable for determination of perfluorosulfonate and perfluorocarboxylate precursors in eggs with high accuracy and sensitivity. It could also be applied to human burden studies of these precursors.

Abstract  The fabrication of lubricants-infused textured surfaces has opened up a new route towards omniphobicity. However, achieving a homogeneous thin film of lubricating material on a flat/smooth surface still remains a challenge. This work shows the successful fabrication of a thin, transparent, and homogeneous coating of perfluoropolyether (PFPE, a lubricating material) on a smooth glass surface by the electrospraying technique. The sol-gel solution for electrospraying was prepared by adding a small amount of (tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-trichlorosilane (FTS) with PFPE which was subsequently electrosprayed on a glass substrate. After curing the coated samples at 80 degrees C, a transparent, homogeneous, and slippery coating with a low surface energy (12.5 mN m(-1)) was obtained. It was observed that the presence of FTS with PFPE, assisted significantly in the stacking of PFPE on the substrate resulting in the formation of smooth, uniform blended (PFPE + FTS) films. The surface nature of the blended films was characterized by spectroscopy and microscopy. The blended surface exhibited omniphobic properties. The surface contact angles and slipping angles made by water and acetone droplets were measured to be (116 degrees, 40.8 degrees) and (6 degrees, 10 degrees), respectively. Furthermore, the coating showed good optical (transmittance -91%) and mechanical properties with strong adherence to glass surfaces, thus revealing the potential for applications in windows and solar modules.

Abstract  This work investigated the bioconcentration of PFASs in juvenile rainbow trout by exposing the fish in separate tanks under flow-through conditions to water continuously spiked with either of the AFFFs FC-203CF light water AFFF 3% (3M) or Niagara 1-3 (Angus Fire); a nonspiked tank served as the control. Three fish in each tank were collected after 1, 3, 6, and 11 days of exposure, and 3, 7, 14, and 25 days of depuration. Liver and carcass homogenate samples were analyzed for 20 PFASs using LC-MS/MS. PFDS, PFOS, PFHxS, and EtFOSAA were detected in fish exposed to the 3M foam, while 6:2 and 8:2 FTSASs, 6:2 and 8:2 FTSAs, 5:3 and 7:3 FTCAs were measured in fish exposed to Angus Fire foam. Bioconcentration factors and rate constants for uptake and depuration were calculated. Total and extractable organofluorine were measured in the fish samples. After fish were exposed to AFFFs, not only known PFASs but also other unknown organofluorines were bioconcentrated. Compared to the control group, significantly greater amounts (at least 10-fold) and proportion of unidentified PFASs were found in both liver and carcass homogenate ranging from ∼50% in 3M foam up to 95% in the Angus Fire foam at the end of exposure.

Abstract  The aim of this study was to determine the viability of electrochemical oxidation to degrade and mineralize poly and perfluoroalkyl substances (PFASs) in wastewaters from an industrial facility dedicated to the production of side-chain-fluorinated polymers and fluorotelomer-based products for fire-fighting foams. 6:2 fluorotelomer sulfonamide allcylbetaine (6:2 FTAB, 1111 mu g/L), 6:2 fluorotelomer sulfonic acid (6:2 FTSA, 242.5 mu g/L) and 6:2 fluorotelomer sulfonamide propyl N,N dimethylamine (M4, 34.4 mu g/L) were the most abundant PFASs in the industrial wastewater, that also contained perfluorocarboxylic acids (Sigma PFCAs, 12.2 mu g/L), high TOC and chloride as main anion. 2 L samples were treated in bench scale experiments performed at a current density of 50 mA/cm(2), in a commercial cell equipped with a boron doped diamond (BDD) anode (70 cm(2)). 97.1% of the initial PFASs content was removed after 8 h of electrochemical treatment. Furthermore, the TOC removal (82.5%) and the fluoride release confirmed the PFASs mineralization. Based on the evolution of the different PFASs, electrochemical degradation pathways were proposed. Fluorotelomers sulfonamides 6:2 FTAB and M4 would be degraded into 6:2 FTSA, which conversely would give rise to PFHpA and preferentially PFHxA. The latter PFCAs were transformed into shorter-chain PFCAs, and eventually into CO2 and fluoride. The reported results support the technical viability of BDD electrooxidation for the treatment of PFASs in industrial wastewater.

Abstract  Environmental context Polyfluorinated substances are anthropogenic chemicals that have been widely used in several industrial and commercial applications. Analysis of human plasma samples collected from Munster in Germany revealed, since the year 2000, increasing amounts and proportion of unidentified organofluorines. The increasing trend of unidentified organofluorines in plasma samples suggests that humans are being exposed to new and unidentified fluorinated products.

Abstract Samples of human plasma (n=122) from two German cities (collected in 1982-2009, excluding 1994) and whole blood (n=47) from seven Chinese cities (collected in 2004) were analysed for 52 polyfluoroalkyl/perfluoroalkyl substances (PFASs) using LC-MS/MS. Quantifiable PFASs included some newly identified and commercially available chemicals PFPAs, PFPiAs, FTSAs, PAPs and di-SAmPAP, metabolites of fluorotelomer-based products (FTCAs/FTUCAs), PFCAs, PFSAs, FASAs and FOSAAs. The blood samples were also analysed for extractable organofluorine (EOF) using total organofluorine combustion ion chromatography (TOF-CIC). Seven more PFASs (C7 and C10 PFSAs, FOSAA, MeFOSAA, EtFOSAA, C13 PFCA and 8:2 FTSA) were detected in the Chinese samples than had been previously reported. For the German samples, PFHpS, FOSA, MeFOSA, EtFOSA, FTSAs (6:2, 8:2), PFPAs (C6, C8) and PFPiAs (C6/C6, C6/C8, C8/C8) were additional chemicals identified that were not measured in the earlier studies. Those newly identified and commercially available PFASs were either at trace levels (pg mL(-1)) or not detected. A mass balance of fluorine between quantifiable PFAS and EOF in the Chinese samples indicated quantifiable PFASs accounted for 31-86% of EOF. For the German samples, the quantifiable PFAS accounted for 52-100% and 57-100% of EOF in Munster and Halle samples respectively. After the year 2000, an increasing amount and proportion of unidentified organofluorine were observed in Munster samples. The increasing trend of unidentified organofluorine in plasma samples suggested humans are being exposed to new and unidentified fluorinated products.

Abstract  OBJECTIVES: The aim of this study was to evaluate the safety and effectiveness of a fast-track surgery (FTS) protocol on patients undergoing minimally invasive oesophagectomy.

METHODS: We retrospectively analysed the clinical data of 80 eligible patients who underwent elective minimally invasive oesophagectomy in our department from January 2012 to April 2013 by the same surgical team. Two groups of these patients were compared. The control group comprised patients treated with traditional methods. Clinical parameters were compared. The study group was formed by patients treated with the fast-track concept, such as (i) a semi-liquid meal was administered up to 6 h before surgery and the patients were made to drink 200 ml of 10% glucose solution 3 h before surgery; (ii) no nasogastric tube, no abdominal drainage tube and no draining sinus in the neck; (iii) the chest tube and catheter were removed as early as possible; (iv) prevention of hypothermia therapy; (v) an attempt at bedside rehabilitation on postoperative day (POD) 2; and (vi) early postoperative enteral nutrition, restrictive intravenous fluids intraoperatively and postoperatively, and oral feeding initiated 48 h after surgery.

RESULTS: There were no significant differences between the two groups with regard to age, sex, pathologic tumor-node-metastasis stage, tumour location, pathology, American Society of Anesthesiologists score, preoperative albumin level, 30-day readmission or complications (P >0.05). Compared with the conventional group, the FTS group had earlier first flatus [(3 (3-4) vs 6 (6-7) days], less fluid transfusion [2.1 (2.06-2.2) vs 2.8 (2.7-2.9) l] and shorter postoperative hospital stay [7 (6-9) days vs 12 (10-16.5) days] (P <0.05). There was no difference between the two groups with regard to vomiting, but patients in the conventional group suffered from/experienced pharyngitis considerably more than the FTS group (P <0.001).

CONCLUSIONS: FTS on patients with oesophageal cancer receiving minimally invasive oesophagectomy is safe, feasible and efficient, and can accelerate postoperative rehabilitation. Compared with the conventional protocol, its advantages were limited to short-term follow-up.

Abstract  We report on a fast, accurate and rugged analytical procedure to determine a wide span of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in seabird plasma. The 26 investigated compounds included perfluoroalkyl carboxylates (C5-C14 PFCAs), perfluoroalkyl sulfonates (C4, C6, C7, C8, C10 PFSAs), perfluorooctane sulfonamide (FOSA) and N-alkyl derivatives (MeFOSA, EtFOSA), N-alkyl perfluorooctane sulfonamido acetic acids (MeFOSAA, EtFOSAA), fluorotelomer sulfonates (4:2 FTSA, 6:2 FTSA, 8:2 FTSA), polyfluoroalkyl phosphate diesters (diPAPs) and perfluorooctane sulfonamide phosphate diester (diSAmPAP). The method described herein requires a reduced sample amount (25μL) and involves rapid and simple sample preparation (protein precipitation with acetonitrile but without acidification) prior to analysis by on-line solid phase extraction (Oasis HLB sorbent) coupled to high performance liquid chromatography negative electrospray ionization tandem mass spectrometry. The optimization was conducted using experimental designs to account for potential interactions between variables. Out of the 26 target analytes, 23 compounds showed excellent accuracy (±25% of the expected values). Intermediate precision and matrix effects remained acceptable for most analytes thanks to efficient internal standardization. A human serum standard reference material (NIST SRM 1957) was included in the validation scheme to evaluate method trueness, which proved satisfactory (│Z-scores│<2 for most compounds). Notwithstanding the small initial sample intake, limits of detection as low as 0.003-0.1ngg(-1) plasma were obtained. This allowed the determination of 11 target PFASs in Antarctic seabird plasma samples. ΣPFASs in Antarctic seabird plasma ranged from 0.37 to 19ngg(-1), with a predominance of PFOS (>54% of ΣPFASs on average). The reduced plasma amount required implies that the present method could also be applied to the analysis of PFASs in the plasma of smaller biological models.

Abstract  Perfluoroalkyl acids (PFAAs) precursors, the indirect source of PFAA exposure, have been observed in environmental and human samples. However, the maternal-fetal transfer of these chemicals has not been well examined. In this study, 50 paired maternal and cord serum samples collected in Jiangsu province of China were analyzed for fifteen PFAA precursors. Among the detected PFAAs, 6:2 fluorotelomer sulfonate (6:2 FTS), N-methyl- and N-ethyl-perfluorooctanesulfonamidoacetates had comparable detection rate in both maternal and cord sera, while the mean concentrations and detection rates of 8:2 FTS and perfluorooctane sulfonamide (PFOSA) were higher in maternal sera compared to cord sera (Mann-Whitney U test, P < 0.05). Analysis of variance and least significant difference tests showed that the youngest maternal age group (21-24 years old) had the highest concentration of 6:2 FTS in cord sera. Maternal serum PFOSA was found significantly correlated with the cord serum perfluorooctanesulfonate (PFOS) (Spearman test, r = 0.361, P = 0.010), indicating that maternal serum PFOSA might be an indirect source of PFOS in fetuses. The obtained results suggested the potential prenatal exposure and human placental transfer of perfluoroalkyl acid precursors.

Abstract  On July 6th 2013, an unmanned train laden with almost 8 million liters of crude oil careened off the rails downtown Lac-Mégantic (Québec, Canada). In the aftermath of the derailment accident, the emergency response entailed the deployment of 33 000 L of aqueous film forming foam (AFFF) concentrate that contained proprietary fluorosurfactants. The present study examines the environmental occurrence of perfluoroalkyl acids (PFAAs) and newly identified per and polyfluoroalkyl substances (PFASs) in the benthic fish white sucker (Catostomus commersonii) and sediments from Lake Mégantic and Chaudière River. In sediments, PFAAs displayed relatively low concentrations (∑PFAAs = 0.06–0.5 ng g–1 dw) while the sum of fluorotelomer-based PFASs was in the range < LOD–6.2 ng g–1 dw. Notably, fluorotelomer sulfonamide betaines (8:2-FTAB and 10:2-FTAB), fluorotelomer betaines (9:3-FTB, 11:3-FTB and 9:1:2 FTB) and 6:2 fluorotelomer sulfonate (6:2-FTSA) were ubiquitously identified in the sediment samples surveyed. Levels of PFAAs remained moderate in fish muscle (e.g., PFOS: 0.28–2.1 ng g–1 wet-weight), with little or no differences when comparing 2013 or 2014 fish samples with 2011 archived samples. In contrast, n:2-FTSAs emerged in the immediate weeks or months that followed the accident, as did several betaine-based PFASs (8:2-FTAB, 10:2-FTAB, 9:3-FTB, 11:3-FTB, 7:1:2 FTB and 9:1:2 FTB), observed for the first time in situ. Fluorotelomer thioether amido sulfonate (10:2-FTSAS) and fluorotelomer sulfoxide amido sulfonate (10:2-FTSAS-sulfoxide) were also occasionally reported after the AFFF spill. With time, levels of betaine-based PFASs gradually decreased in fish, possibly indicating attenuation by biodegradation of the fluorine-free moiety, supported by the observation of likely metabolites such as n:3-fluorotelomer carboxylates and n:2-fluorotelomer sulfonamides.

Abstract  This paper reports the electrochemical treatment of poly- and perfluoroalkyl substances (PFASs) in the effluent from an industrial wastewater treatment plant (WWTP). While most of the previous research focused on the electrochemical degradation of perfluorooctanoic acid and perfluorooctane sulfonate in model solutions, this work studies the simultaneous removal of 8 PFASs at environmentally relevant concentrations in real industrial emissions, which also contained organic matter and inorganic anions. The overall PFASs content in the WWTP effluent was 1652 mu g/L, which emphasized the need to develop innovative technologies for the management of PFASs emissions. 6:2 fluorotelomer sulfonamide allcylbetaine (6:2 FTAB) and 6:2 fluorotelomer sulfonate (6:2 FTSA) were the major contributors (92% w/w) to the overall PFASs content, that also contained significant amounts of short-chain perfluorocarboxylic acids (PFCAs). Using a boron doped diamond (BDD) anode of 0.0070 m(2), the effluent (2 L) was treated by applying a current density of 50 mA/cm(2) for 10 h, that resulted in 99.7% PFASs removal. The operation at lower current densities (5 and 10 mA/cm2) evidenced the initial degradation of 6:2 fluorotelomers into perfluoroheptanoic and perfluorohexanoic acids, that were later degraded into shorter chain PFCAs. The high TOC removal, >90%, and the fluoride release revealed that PFASs mineralization was effective. These results highlight the potential of the electrochemical technology for the treatment of PFASs contained in industrial wastewaters, which nowadays stands as the main source of this group of persistent pollutants into the environment. (C) 2017 Elsevier B.V. All rights reserved.

Abstract  UNLABELLED: In order to achieve enhanced and synergistic delivery of paclitaxel (PTX), a hydrophobic anticancer agent, two novel prodrug copolymers, POEG15-b-PFTS6 and POEG15-b-PFTS16 composed of hydrophilic poly(oligo(ethylene glycol) methacrylate) (POEG) and hydrophobic farnesylthiosalicylate (FTS, a nontoxic Ras antagonist) blocks, were synthesized. Both POEG-b-PFTS polymers were able to form micelles with intrinsic antitumor activity in vitro and in vivo. Employing these micelles as a carrier to load PTX, their drug loading capacity, stability, in vivo biodistribution and tumor inhibition effect were evaluated. PTX/POEG15-b-PFTS16 mixed micelles exhibited an excellent stability of 9days at 4°C with a PTX loading capacity of 8.2%, which was more effective than PTX/POEG15-b-PFTS6 mixed micelles. In vivo biodistribution data showed that DiR-loaded POEG-b-PFTS micelles were more effectively localized in the tumor than in other organs. Moreover, both PTX/POEG-b-PFTS micelles showed significantly higher antitumor activity than Taxol in a 4T1.2 murine breast tumor model, and the tumor inhibition and animal survival followed the order of PTX/POEG15-b-PFTS16>PTX/POEG15-b-PFTS6>POEG15-b-PFTS16>Taxol≈POEG15-b-PFTS6. Our data suggest that POEG-b-PFTS micelles are a promising anticancer drug carrier that warrants more studies in the future.

STATEMENT OF SIGNIFICANCE: Polymerization of drug-based monomer represents a facile and precise method to obtain well-defined polymeric prodrug amphiphiles. Currently, most reports largely focus on the synthesis methods and the biophysical properties. There is limited information about their anti-tumor activity and delivery function as prodrug carriers in vitro and in vivo. In this manuscript, we report the development of two novel prodrug copolymers, POEG15-b-PFTS6 and POEG15-b-PFTS16 composed of hydrophilic poly(oligo(ethylene glycol) methacrylate) (POEG) and hydrophobic farnesylthiosalicylate (FTS, a nontoxic Ras antagonist) blocks. Both POEG-b-PFTS polymers were able to self-assemble into nano-sized micelles with intrinsic antitumor activity in vitro and in vivo. More importantly, POEG-b-PFTS polymers were effective in forming stable mixed micelles with various anticancer agents including PTX, DOX, docetaxel, gefitinib, and imatinib. Delivery of PTX via our new carrier led to significantly improved antitumor activity, suggesting effective PTX/FTS combination therapy. We believe that our study shall be of broad interest to the readers in the fields of biomaterials and drug delivery.

Abstract  The distribution of polyfluoroalkyl compounds (PFCs) in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied. The PFCs quantified included C4-C8 perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C6 and C8 perfluorinated sulfinates (PFSiAs), C4-C12 perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m2-PFOA), perfluorooctane sulfonamide (FOSA), and n-ethyl perfluroctane sulfonamidoethanol (EtFOSE). PFCs were mostly distributed in the dissolved phase, where perfluorooctanoic acid (PFOA) dominated with 2.9--12.5 ng/L. In the suspended particulate matter FOSA and perfluorooctane sulfonate (PFOS) showed the highest concentrations (4.0 ng/L and 2.3 ng/L, respectively). The total flux of capital sigma PFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase. This indicates that the river Elbe acts as a source of PFCs into the North Sea. However, the concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) in the North Sea were higher than that in the river Elbe, thus an alternative source must exist for these compounds.

Abstract  The treatment of fluorosurfactant-containing wastewater is still challenging nowadays. Here, a method is presented to remove fluorosurfactants from water, amongst others from electroplating wastewater. This elimination technique is based on the generation of gas bubbles in solution, enrichment and scavenging of fluorosurfactants by transport of the gas bubbles to the water surface. Finally the bubbles collapse and release an aerosol which is enriched with fluorosurfactants. By sampling of the released aerosols a mass balance was established for 6:2 fluorotelomer sulfonic acid (6:2 FTSA). Thereby 99.8% of the initial amount was revocered in the collected aerosols. Fluorosurfactant concentration in solution decreased exponentially with half-lives ranging from 2 to 6 min for 6:2 FTSA as well as perfluorooctane carboxylate (PFOA) and perfluorooctane sulfonate (PFOS). Elimination rate in defined matrix (0.2 M H2SO4) within 60 min was 99.6, 99.9 and 99.8% for 6:2 FTSA, PFOA and PFOS, respectively. The removal rate of 6:2 FTSA increased in solutions with higher ionic strength. Different wastewater from an electroplating industry containing 6:2 FTSA was treated with the described method without any sample pre-treatment and elimination of 6:2 FTSA took place with the same effectiveness as in synthetic matrices.

Abstract  Per- and polyfluoroalkyl substances (PFASs) are a family of compounds that includes numerous compound classes. To date, only a subset of these PFASs have been studied thoroughly in the general population. In this study, pooled serum samples from Australia collected in 2002-2013 were analyzed for PFASs according to gender and age (age categories of 0-4 years, 5-15 years, 16-30 years, 31-45 years, 46-60 years, and >60 years), in total 54 pooled samples and 4920 individuals. Compound classes included were perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs), and two groups of PFCA precursor compounds; polyfluoroalkyl phosphate diesters (diPAPs), and fluorotelomer sulfonic acids (FTSAs). Several PFASs that were not reported in previous studies of Australian serum samples were found in this sample set including; diPAPs, FTSAs, perfluoropentane sulfonic acid (PFPeS), perfluoroheptane sulfonic acid (PFHpS), perfluoroheptane carboxylic acid (PFHpA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and perfluorotridecanoic acid (PFTrDA). Various temporal trends were observed with a significant reduction (p < 0.05) between 2002 and 2013 for 8:2 FTSA, perflurohexane sulfonic acid (PFHxS), PFHpS, PFOS, and perflurooctanoic acid (PFOA). Levels of longer-chained PFDA and PFUnDA started to decrease more recently, between 2006 and 2013, while PFDoDA increased during the same time period. Higher levels in younger age groups (0-4 and 5-15 years) compared to adults (>15 years) were found for 8:2 FTSA and PFHpA, while levels of PFHpS, PFOS, PFUnDA, PFDoDA and PFTrDA were higher in adult age groups compared to younger age groups. Gender-specific patterns were seen for PFOA, PFHxS, PFHpS and PFOS, where levels were lower in women. Changes in manufacturing processes were reflected in the temporal time trends, and differences in bioaccumulation potential between homologues could be associated with age trends. Our results emphasize the importance of including emerging classes of PFASs in biomonitoring studies.

Abstract  Aerobic biodegradation of 8:2 fluorotelomer stearate (FTS) and 8:2 fluorotelomer citrate triester (TBC) was evaluated in a forest soil in closed bottle microcosms. Loss of parent, production of 8:2 fluorotelomer alcohol (8:2 FTOH), which is released along with stearic acid (SA) by microbial ester linkage, and subsequent metabolites from FTOH degradation were monitored for up to 7months. Soil microcosms were extracted with ethyl acetate followed by two heated 90/10 v/v acetonitrile/200mM NaOH extractions. Cleavage of the ester linkage in the 8:2 FTS occurred (t1/2∼28d), producing 8:2 FTOH and various levels of subsequent metabolites. Quantifying the generation of SA from ester cleavage in FTS was complicated by the natural production and degradation of SA in soil, which was probed in an additional FTS and SA study with the same soil that had been stored at 4°C for 12months. In the latter study, FTS degraded faster (t1/2∼5d) such that SA production well above soil background levels was clearly observed along with rapid subsequent SA degradation. Cold storage was hypothesized to enrich fungal enzymes, which are known to be effective at hydrolytic cleavage. 8:2 TBC biotransformation was slow, but evident with the production of PFOA well above levels expected from known FTOH residuals. Slower degradation of TBC compared to FTS is likely due to steric hindrances arising from the close proximity of three 8:2 FT chains on the citrate backbone limiting the enzyme access.

Abstract  The aerobic biotransformation pathways of 4:2, 6:2, and 8:2 fluorotelomer thioether amido sulfonate (FtTAoS) were characterized by determining the fate of the compounds in soil and medium microcosms amended with an aqueous film-forming foam (AFFF) solution. The biotransformation of FtTAoS occurred in live microcosms over approximately 40 days and produced 4:2, 6:2, and 8:2 fluorotelomer sulfonate (FtS), 6:2 fluorotelomer unsaturated carboxylic acid (FtUCA), 5:3 fluorotelomer carboxylic acid (FtCA), and C4 to C8 perfluorinated carboxylic acids (PFCAs). Two biotransformation products corresponding to singly and doubly oxygenated forms of 6:2 FtTAoS were also identified through high resolution mass spectrometry (MS) analysis and liquid chromatography tandem-MS. An oxidative assay was used to indirectly quantify the total concentration of polyfluorinated compounds and check the mass balance. The assay produced near complete mass recovery of FtTAoS after biotransformation, with 10% (mol/mol) of the amended FtTAoS accounted for in FtS, FtCA, and PFCA products. The transformation rates of identified products appear to be slow relative to FtTAoS, indicating that some intermediates may persist in the environment. This study confirms some of the sources of FtS and PFCAs in groundwater and soil at AFFF-impacted sites and suggests that fluorinated intermediates that are not routinely measured during the biotransformation of PFASs may accumulate.

Abstract  Cytomegalovirus (CMV) has recently been suggested as a potential risk factor for the development of ectopic pregnancy (EP) following upper genital tract infection in women. However, little is known about its associated underlying pathogenic mechanisms. This was a prospective case-control study that measured the prevalence of CMV infection in Fallopian tubes (FT) bearing an EP and its effects on the tubal expression of interleukin (IL)-6 and its signaling molecules, which are known to play significant roles in the immune response against CMV infection as well as embryo implantation. Fresh FTs from 96 EPs during salpingectomy and another 61 women at the midluteal phase during total abdominal hysterectomy (TAH) were collected to measure the rate of CMV by an IVD CE PCR kit. The participants were then classified to measure the expression of IL-6, its receptor (IL6R) and intracellular mediators (gp-130, STAT3) by immunohistochemistry and quantitative RT-PCR. The results showed significantly higher (P = 0.01) rates of CMV in FTs obtained from EP (22.9 %) compared with controls (8.2 %). IL-6 (P = 0.003), IL6Rα (P = 0.02), gp 130 (P = 0.008) and STAT3 (P = 0.03) were significantly higher in TAH-positive (n = 5) compared with TAH-negative FTs by immunohistochemistry. Furthermore, the expression in the non-infected EP samples was significantly higher for IL-6 (P = 0.004), IL6R (P = 0.007), gp130 (P = 0.006) and STAT3 (P = 0.007) compared with negative TAH. Similar results were observed by quantitative PCR. CMV-positive EP samples showed the highest significant increase of the studied molecules by all techniques. In conclusion, Fallopian tubal infection with CMV is higher in EP and could predispose to embryo implantation by up-regulating the expression of IL-6 and its related molecules as part of tubal innate immune response. Further in vitro and in vivo studies are compulsory to illustrate the roles of IL-6 and CMV in the pathogenesis of EP.

Abstract  Previously, much of the perfluoroalkyl and polyfluoroalkyl substance (PFAS) research has focused on perfluoroallcyl carboxylates (PFCAs) or perfluoroalkane sulfonates (PFSAs). Recent studies indicate that known PFCAs and PFSAs accounted for 5-95% of the organofluorine (OF) in human and wild rat blood samples suggesting that a relatively large proportion of OF remained unknown. Until recently, some studies reported commercially available compounds such as polyfluoroalkyl phosphate diesters (diPAPs) and fluorotelomer sulfonates (FTSAs) in human blood and sludge samples. The present investigation is a pilot study aiming at surveying some newly identified PFASs such as diPAPs, FTSAs, and perfluorinated phosphinates (PFPiAs) in different environmental samples including surface water, sediment, sewage treatment plant influent and effluent, sludge, benthic worm, and human blood from Hong Kong. DiPAPs (6:2, 6:2/8:2, and 8:2) were detected in some of the samples at part-per-billion (ppb) levels in sludge, sub ppb levels in influent and effluent, sediment, worm, and human blood samples, and sub part-per-trillion (ppt) levels in surface waters. Sub ppt to ppb levels of 6:2 and 8:2 FTSAs were observed in worm, surface water, and human blood samples. PFPiAs were only observed in worm samples. The detected "new PFASs" accounted for a minor proportion (less than 5%) of the total PFASs in benthic worm and human blood, but up to 95% in sewage sludge samples from Hong Kong. This is the first report of commercial fluorosurfactants (PFPiAs, diPAPs, and FTSAs) in the samples from the environment and human blood in Hong Kong; further information on the distribution, fate, and transport of "new PFASs" in other Asian cities, as well as toxicity, is needed for further assessing the human exposure and risk.

Abstract  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.