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The perfluorooctane sulfonate alternative, F-53B, induces multiple physiological defects but whether it can disrupt eye development is unknown. We exposed zebrafish to F-53B at four different concentrations (0, 0.15, 1.5, and 15 μg/L) for 120 h post-fertilization (hpf). Locomotor behavior, neurotransmitters content, histopathological alterations, morphological changes, cell apoptosis, and retinoic acid signaling were studied. Histology and morphological analyses showed that F-53B induced pathological changes in lens and retina of larvae and eye size were significantly reduced as compared to control. Acridine orange (AO) staining revealed a dose-dependent increase in early apoptosis, accompanied by upregulation of p53, casp-9 and casp-3 genes. Genes related to retinoic acid signaling (aldh1a2), lens developmental (cryaa, crybb, crygn, and mipa) and retinal development (pax6, rx1, gant1, rho, opn1sw and opn1lw) were significantly downregulated. In addition, behavioral responses (swimming speed) were significantly increased, while no significant changes in the neurotransmitters (dopamine and acetylcholine) level were observed. Therefore, in this study we observed that exposure to F-53B inflicted histological and morphological changes in zebrafish larvae eye, induced visual motor dysfunctions, perturbed retinoid signaling and retinal development and ultimately triggering apoptosis.

Perfluoroalkyl substances (PFASs) are persistent organic pollutants that may lead the adverse birth outcomes, including preterm birth (PTB). However, previous studies have reported inconsistent results on the association between PFASs and PTB, and lack of the epidemiological evidence regarding the effect of PFASs mixture on PTB. This study aimed to explore association of individual and multiple exposure to PFASs with PTB.The study subjects were consisted of 1341 pregnant women from Guangxi Zhuang Birth Cohort in Guangxi, China, from June 2015 to April 2019. Nine PFASs concentrations in the maternal serum were examined by ultrahigh liquid performance chromatography-tandem mass spectrometry, and the gestational weeks were obtained from medical records. We applied binary logistics regression model to explore correlation between individual PFAS and PTB and inspected the combined effect of PFASs mixture on PTB by applying Bayesian kernel machine regression (BKMR) and weighted quantile sum (WQS) regression models.In adjusted logistics regression model, perfluorooctane sulfonate (PFOS), perfluoroheptanoic acid (PFHpA), perfluorobutanesulfonic acid (PFBS), ∑perfluorinated sulfonic acids (PFSA), and ∑PFASs were positively associated with the risk of PTB. In contrast, perfluoroundecanoic acid (PFUnA), perfluorohexane sulfonate (PFHxS), and perfluorooctanoic acid (PFOA) were negatively associated with the risk of PTB. These associations of n PFOS and PFHpA with PTB were found to be more pronounced in male infants. Restricted cubic splines (RCSs) showed an inverse U-shaped relationship between PFBS and PTB. Analysis from BKMR model showed a positive association between PFASs mixture and PTB, and no evidence of interactions among the nine PFASs were detected. Additionally, PFHpA, PFOS, and PFBS were identified as the main contributors for the effect of PFASs mixture on increasing the risk of PTB by BKMR and WQS models.Prenatal exposure to higher levels of PFASs mixture was associated with higher risk of PTB.

The poly (methyl methacrylate) (PMMA)-based nanoparticle was synthesized by surfactant-free emulsion polymerization method and then post modified with Calixarene using (3-Aminopropyl)triethoxysilane organo-silane as a linker after OH-treatment. The prepared structure was applied for efficient adsorption of Vanadium ions in the aqueous solution after characterization by FT-IR, SEM, TEM, DLS, and EDX. Additional investigations discovered that the prepared adsorbent has a good capacity to adsorb vanadium ions. The effect of key experimental factors was studied to find the optimal point of adsorbent efficiency including the initial concentration of analyte, sorbent dosage, pH of the solution, contact time, and type/quantity of the eluents. It was specified, the maximum adsorption capacity for the synthesized nanoparticles was obtained about 322 mg g

The present study investigated the roles of peroxydisulfate (PDS) radicals and sulfate radicals (SO

Per-/polyfluoroalkyl substances (PFASs) are ubiquitous in the environment and have been proved to be immunotoxic to humans. However, it remains unclear whether exposure to PFASs affects the risk of rheumatoid arthritis (RA). In this study, nine PFASs were determined in human serum collected from 280 health populations and 294 RA patients in a cohort enrolled between 2018 and 2020 in Hangzhou, China, and were examined their correlations with immune marker levels. Perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) were the predominant PFASs in human serum, with median (mean) concentrations of 5.4 (7.6), 2.8 (3.5), and 1.9 (2.5) ng/mL, respectively. Serum PFOA and 6:2 Cl-PFESA concentrations were positively correlated with anti-cyclic citrullinated peptide antibody (ACPA) (β

Electroplating industry is an important application field of per- and polyfluoroalkyl substances (PFASs) as the chromium mist suppressants. 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFAES) and perfluorooctanesulfonate (PFOS) have been the two widely used mist suppressants, and after the ban of PFOS, 6:2 Cl-PFAES will become the dominant suppressant. The behavior and mechanisms of 6:2 Cl-PFAES in the electroplating industry and the receiving environment were studied and compared with PFOS. 6:2 Cl-PFAES behaved similarly with PFOS due to their similar chemical structure. However, some difference exists for the relatively stronger hydrophobicity of 6:2 Cl-PFAES. Up to 35.7 mg/L of PFOS and 13.4 mg/L of 6:2 Cl-PFAES were found in the industrial wastewater influents, and were effectively reduced to 0.3-0.8 mg/L by the interaction with chromium hydroxide through hydrophobic interaction and ligand exchange. The stronger hydrophobicity of 6:2 Cl-PFAES than PFOS resulted in its accumulation in the surface of foams and comparable or less removal during the industrial and municipal wastewater treatment. 6:2 Cl-PFAES exhibited higher bioaccumulation potential than PFOS in the surface water. 6:2 Cl-PFAES emitted by both mists and water may pose health risks to humans. More attentions towards 6:2 Cl-PFAES are needed after the replacement of PFOS by it in the electroplating industry as a global contaminant of emerging concerns.

6:2 chlorinated polyfluorinated ether sulfonate (F-53B), a Chinese PFOS alternative, has recently been identified in the aquatic environment at concentrations similar to or higher than perfluorooctane sulfonate (PFOS). Although previous studies have shown that F-53B can trigger oxidative stress in fish, the underlying molecular mechanism is still largely unknown. In this study, zebrafish embryos were exposed to various concentrations of F-53B (0, 0.5, 20 and 200 μg/L) for 5 d to investigate oxidative stress responses and possible molecular mechanisms of action. Our results showed that F-53B accumulated in a concentration-dependent manner in zebrafish larvae. The contents of malondialdehyde (MDA) and reduced glutathione (GSH), as well as the activities, mRNA and protein levels of most of antioxidant enzyme genes involved in the phosphatidylinositol 3-kinase (PI3K)/Akt/Nrf2-ARE pathway were significantly reduced. Further in silico study indicated that F-53B binds tightly to PI3K, which may be related to the inhibition of Nrf2-regulated antioxidant functions by F-53B as a PI3K inhibitor. Combining in vivo and in silico studies, we elucidated the effects of F-53B on antioxidant system of zebrafish through the PI3K/Akt/Nrf2-ARE pathway, which increases our understanding of the molecular mechanism of F-53B on antioxidant responses in fish.

The wide application of 6:2 fluorotelomer sulfonate (6:2 FTS) and its precursors results in their ubiquitous occurrence in the environment. This study investigated the biotransformation of 6:2 FTS using fresh slurries collected from constructed wetland under aerobic and anoxic conditions. Biotransformation rates of 6:2 FTS was extremely slow under both aerobic and anoxic conditions. The analysis of transformation products showed that less than 0.7 mol% of initial concentration of 6:2 FTS was biotransformed under anoxic conditions. Effects of 6:2 FTS on the shifts in microbial community in wetland slurry during aerobic and anoxic transformation were evaluated using 16S rRNA gene amplicon sequencing. Under aerobic conditions, 6:2 FTS altered the microbial community structure, in which Methylocaldum (Gamma-proteobacteria) became the predominant genus after being exposed to 6:2 FTS. This means that Methylocaldum appears to have higher tolerance to 6:2 FTS and seems to be potential 6:2 FTS-degrading bacteria. Under anoxic transformation, only the genus Methanomethylovorans (Euryarchaeota) was increased remarkably in wetland slurry exposed to 6:2 FTS.

Little information exists on the effects of shipping and handling on per- and polyfluoroalkyl substances (PFASs) in environmental samples. Thus, we evaluated the integrity of dried wastewater extracts and the sensitivity of our high-resolution mass spectrometry (HRMS) instrument to perform such analyses by monitoring 13 representative PFASs in samples extracted, evaporated, and stored at room temperature up to one month. Relative to zero-day recoveries of six detected PFASs ranged between 94 and 124% (RSD 38%) for influents, between 88 and 126% (RSD 18%) for effluents after 28 days. Larger variabilities are tentatively associated with the lack of specific mass-labeled standards and the interactions between analytes and remaining matrix components over time. In a second stage, a mix of local and international dry-shipped wastewater samples were analyzed and the same PFASs were quantified. Up to six PFASs were identified, with median concentrations ranging from 1.3 (perfluoro butyl sulfonate (PFBS)) to 7.7 ng/L (perfluoro hexanoic acid (PFHxA)) and from 1.5 (PFBS) to 13.8 ng/L (PFHxA) in local influents and effluents respectively; and from 0.7 (perfluoro hexyl sulfonate (PFHxS)) to 52.8 ng/L (PFHxA) and from 0.5 (PFHxS) to 21.4 ng/L (PFHxA) in Greek influents and effluents, respectively. The importance of this study lies on the need to consider the wider recovery shifts and expanded variability ranges of PFASs derived from the transport and storage times of dried extracts, particularly when applied to HRMS and wide-scope screening approaches.

There is an urgent need to investigate on the distribution and fate of short-chain analogues and emerging per- and polyfluoroalkyl substances (PFASs) in groundwater, and little research on their source apportionment and health risks through the drinking water exposure pathway has been carried out. In present study, the concentration and source of 22 PFASs, including five alternatives: 6:2 fluorotelomer sulfonate (6:2 FTS), potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate (F–53B), hexafluoropropylene oxide trimer acid (HFPO-TA), hexafluoropropylene oxide dimer acid (HFPO-DA) and ammonium 4, 8-dioxa-3H-perfluorononanoate (ADONA), were analyzed in 88 groundwater samples from wells in Jiangxi Province, southeastern China. The total PFASs concentration (Σ18PFASs) in groundwater varied from 1.27 to 381.00 ng/L (mean 47.60 ng/L). Short-chain perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPeA) were the most abundant PFCAs, and short-chain perfluorobutanesulfonate (PFBS) was the most abundant perfluorinated sulfonic acids (PFSA) in groundwater samples. The quantitative source apportionment by nonnegative matrix/tensor factorization coupled with k-means clustering (NMFk) model suggested that short-chain homologues and emerging alternatives have been used as substitutes for legacy PFOS and PFOA. Furthermore, the human risk assessment results showed that the estimated daily intakes (EDIs) for short-chain PFCAs were higher than that of PFOA, whereas the EDIs of PFBS, 6:2 FTS and F–53B were comparable to that of PFOS.

Biotransformation of 6:2 fluorotelomer sulfonate (FTS) results in the formation of short-chain (C4 – C6) perfluorocarboxylic acids (PFCAs) in landfill leachate. Although leachate substrate concentrations (i.e., organic carbon, ammonia) vary widely, their effects on 6:2 FTS biotransformation and PFCAs formation are unknown. This study investigated the effect of organic carbon and ammonia concentration in 6:2 FTS aerobic biotransformation and PFCA formation in leachate. Biotransformation experiments were conducted with sediment collected from a landfill leachate ditch, to which deionized (DI) water and various amounts of leachate were added. Microbial community analysis using 16S rRNA indicated that while phylum Proteobacteria dominated the bacterial composition throughout the 60 days, Actinobacteria increased with time. Many genera from Proteobacteria and Actinobacteria can synthesize a wide array of enzymes, indicating that these phyla are likely to play an important role in 6:2 FTS biotransformation. Higher biotransformation of 6:2 FTS was observed in leachate-added microcosms (∼21%), compared to DI water microcosm (∼14%), likely reflecting the substrate dependency of 6:2 FTS biotransformation. Substrate limiting conditions in DI water microcosm resulted in slightly greater formation of ∑(C4 – C6) PFCAs (∼14 mol%), compared with leachate added microcosms (10–13 mol%). The findings suggest that dilution of landfill leachate, (e.g., during wet seasons), likely results in reduced 6:2 FTS biotransformation and increased PFCAs formation compared to dry conditions. Observed formation of C7 – C8 PFCAs in the live microcosms suggested that landfills act as secondary sources of legacy PFCAs (e.g., perfluorooctanoic acid) in the environment.

Chlorinated polyfluoroalkyl ether sulfonates (trade name F-53B) has been detected in various environmental matrices, and reported to be equally or more toxic than perfluorooctane sulfonate. Efficient sorptive removal of F-53B from water by two types of layered double hydroxides (LDHs), NO3−-LDH and sodium dodecyl sulfate modified NO3−-LDH (SDS-LDH), was demonstrated in this study. Both LDHs removed F-53B in several minutes and had sorption capacities of over 860 mg/g. SDS-LDH exhibited a greater F-53B uptake than NO3−-LDH under the influence of different solution chemistry, including pH 3-11, or in the presence of competing anions or co-contaminants, primarily due to the higher surface areas and the presence of SDS for SDS-LDH. Batch experiments, structural characterization, molecular dynamics simulations, and density functional theory calculations were combined to explore the sorption mechanisms, which mainly include ion exchange (specifically, O-H⋯O/F hydrogen bond), C-F/Cl⋯H hydrogen bond, and micellar sorption (occurring at high initial F-53B concentrations). Accordingly, we propose to improve the sorption performance of LDHs by increasing their surface areas and modifying LDHs to produce more hydrogen bond sites, as well as exfoliating LDHs into two dimensional nanosheets to eliminate the steric hindrance for the micellar formation of F-53B or other per- and polyfluoroalkyl substances.

Recently, a new sustainable anionic surfactant called bio-based internal olefin sulfonate (Bio IOS) has been developed. This surfactant enables excellent water solubility and high surface activity. It has a unique structure of long hydrophobic alkyl chains (C16 to C18) with two types of hydrophilic groups in its midsection, which distinguish it from other conventional anionic surfactants. However, the effects of the specific structural features of the surfactant on its environmental properties and the consequent effects on the environment remain unclear. In this study, we investigated the environmental fate and ecotoxicity of Bio IOS and the effects of the types and positions of hydrophilic groups on biodegradability and ecotoxicity. Biodegradation studies demonstrated that Bio IOS was readily biodegradable with >99.5% removal in wastewater treatment activated sludge (test concentration: 1 mg/L) and a fast half-life of 5.8 h in river water (test concentration: 10 μg/L); the excellent biodegradability was likely due to the high water solubility attributed to the internal hydrophilic groups. Meanwhile, moderately toxic effects were observed, whereby the 50% lethal and effect concentrations of the three freshwater species were above 1 mg/L. Ecotoxicity studies with different types and positions of hydrophilic groups revealed that hydroxyalkane sulfonate was less toxic and that toxicity was reduced in the presence of more internally located hydrophilic groups. These findings suggest that the hydroxyl group and the internal positions of hydrophilic groups that constitute the molecular configuration resembling two separate shorter alkyl chains may reduce the adverse effects on organisms despite the long alkyl chains.

The Yellow Sea (YS), the East China Sea (ECS) and their coastal areas have undergone rapid urbanization and industrialization. These areas are important sinks for many persistent organic pollutants. In this study, the concentration of legacy and emerging per- and polyfluoroalkyl substances (PFAS) in marine sediments from the YS and ECS were investigated. Nineteen PFAS were identified, ranging in concentration from 0.21 ng/g to 4.74 ng/g (mean: 1.60 ng/g). Legacy long-chain PFAS [e.g., perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS)] were the dominant contaminants. Alternative PFAS such as 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) and 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy) propanoic acid (HFPO-DA) were identified within the detection range of 16%–100%. HFPO-DA was measured in all sediments in equivalent levels to PFOS (0.119 ng/g and 0.139 ng/g, respectively). This is the first reported occurrence of perfluoro-1-butanesulfonamide (FBSA) and HFPO-DA in marine sediments, indicating a replacement in the production of PFAS from legacy to emerging ones along with eastern coastal cities of China. The results of the potential source identification demonstrated that metal plating plants, textile treatments, fluoropolymer products, food packaging, and the degradation of volatile precursor substances were the main sources of PFAS in the ECS and YS. The environmental risk assessment based on the risk quotient demonstrated that PFOA and PFOS in the ECS and YS may present a low to medium risk at most sampling points.

This work explores the use of supervised machine learning as a tool for identifying the source of per- and polyfluorinated alkyl substances (PFAS) in water samples on the basis of the detected component concentrations. Specifically, the work focuses on distinguishing between PFAS used in aqueous film forming foam (AFFF) fire suppression applications, and PFAS from other sources. The fact that many sites contaminated with legacy PFOS-based AFFF formulations are dominated by perfluorinated sulfonates can make it tempting to naïvely classify samples dominated by perfluorinated sulfonates as being of AFFF origin. However, a large fraction of samples do not follow this pattern, including some of the most important cases, such as legacy PFOS-based AFFF far from its source. Although PFAS composition can vary substantially at a site as a result of mobility differences between components and other factors, the hypothesis driving the work is that compositional patterns created in the environment can be recognized across different sites by machine learning, and used for source allocation. This work builds on earlier preliminary work by the authors based on a small dataset. This work is based on a much larger 8040-sample dataset, and explores different preprocessing approaches, as well as how feature selection impacts classification performance. The results of this work strongly support the idea that supervised machine learning based on composition can identify patterns that can be used to distinguish PFAS sources. The results provide new insights into selection of classifiers and features for source identification based on PFAS sample composition.

Perfluoroalkyl acids (PFAAs) including perfluoroalkyl sulfonates (PFSAs) and perfluoroallcyl 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 Sigma PFAA 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 PFAA5 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. (C) 2016 Elsevier Ltd. All rights reserved. Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/2955]

Chlorinated polyfluoroalkyl ether sulfonate (Cl-PFESA) is a novel alternative of perfluorooctane sulfonate (PFOS). While its health risks remain unknown, there is preliminary evidence of developmental toxicity. In the present study, human bone mesenchymal stem cells (hBMSCs) were used to evaluate the effects of Cl-PFESA at non-cytotoxic concentrations on molecular regulation and cellular function of stem cells compared to PFOS, perfluorohexane sulfonate (PFHxS) and perfluorooctanoic acid (PFOA). Gene profiles of hBMSCs exposed to 100 nM of Cl-PFESA and the other 3 perfluoroalkyl acids (PFAAs) correlated significantly with each other. A total of 261 genes were found to be affected by all 4 compounds. Functional annotation analysis revealed that osteoblast differentiation, ERK1/2, TGFβ and calcium signalling were interfered. Moreover, DUSP mRNA and P-SMAD protein, key factors in ERK and TGFβ/SMAD signaling, were decreased by Cl-PFESA. Furthermore, intracellular calcium image suggested that calcium transients were enhanced by Cl-PFESA with lower effective concentrations and more prolonged induction than PFOS and PFHxS. Immunofluorescence staining confirmed that the stemness marker CD44 was dose-dependently repressed by Cl-PFESA. In the osteogenic differentiation following exposure to 100 nM of Cl-PFESA, both mRNA and protein of RUNX2, a target of multiple osteogenic pathways, was depressed on differentiation day 7. Exposure to Cl-PFESA at human relevant concentrations during a vulnerable period before differentiation posed persistent effects on hBMSCs, with common or even stronger potency compared to PFAAs.

Aqueous film-forming foam (AFFF) products are used in industrial and military firefighting around the globe. These products contain fluoroalkylthioamido sulfonates, fluoroalkylthiobetaine, and other related substances as the major ingredients, which can be biotransformed in the environment to form 6:2 fluorotelomer sulfonate (6:2 FTSA, F(CF2)6CH2CH2SO3-) as one of the major initial biotransformation products. Limited information is available on 6:2 FTSA aerobic biotransformation in activated sludge and pure microbial culture. This is the first study to report 6:2 FTSA biotransformation in aerobic and anaerobic sediment. 6:2 FTSA was rapidly biotransformed in aerobic river sediment with a half-life less than 5 d. Major stable transformation products observed after 90 d included 5:3 Acid [F(CF2)5CH2CH2COOH), 16 mol%), PFPeA [F(CF2)4COOH, 21 mol%] and PFHxA (F(CF2)5COOH, 20 mol%). 6:2 fluorotelomer alcohol [6:2 FTOH, F(CF2)6CH2CH2OH] was readily biotransfomed whereas 6:2 FTSA biotransformation did not occur in anaerobic sediment over 100 d, indicating that the enzymatic desulfonation step limited 6:2 FTSA biotransformation in anaerobic sediment. These results suggest that 6:2 FTSA related products, after release to the aerobic environment, is likely to biodegrade forming 5:3 Acid, PFPeA and PFHxA. This study also indicates that 6:2 FTSA formed from its aforementioned precursors may be persistent in the anaerobic environment after their potential release. This work provides insight to understanding the fate and environmental loading of AFFF-related products and their major transformation products in the environment.

There is growing concern that microplastics (MPs), which act as carriers of other organic contaminants, are mistakenly ingested by aquatic organisms, consequently causing unpredictable adverse effects. In this study, zebrafish larvae (6 d post fertilization) were exposed to either 6:2 chlorinated polyfluorinated ether sulfonate (F–53B), polystyrene microplastics (PS-MPs) or their combination for 7 d to evaluate the effects of the presence of PS-MPs on the bioaccumulation and immunomodulation of F–53B. PS-MPs greatly promoted the sorption of F–53B, which reduced the bioavailability and bioaccumulation of F–53B in zebrafish larvae. F–53B, PS-MPs, or their mixture significantly reduced the body weight of zebrafish larvae. Combined exposure of PS-MPs and F–53B resulted in a significant reduction in superoxide dismutase (SOD) and lysozyme activity, indicating the occurrence of oxidative stress and inflammatory response in zebrafish larvae. The content of malondialdehyde (MDA) and immunoglobulin M (IgM) was not affected by F–53B or PS-MPs, but significantly increased in their combined exposure. Furthermore, co-exposure of F–53B and PS-MPs significantly upregulated the transcripts of pro-inflammatory cxcl-clc and il-1β genes and increased the levels of iNOS protein in zebrafish larvae. In addition, enhanced protein expression of NF-κB paralleled the upregulation in the expression of most immune-related genes, suggesting NF-κB pathway was mechanistically involved in these responses. Collectively, the presence of MPs decreased F–53B bioaccumulation, but induced inflammatory stress in larval zebrafish. These findings highlight the health risks of co-contamination of MPs and F–53B in aquatic environments.

Contamination by per- and polyfluoroalkyl substances (PFASs) is of great concern in global environments. Due to strong regulation of legacy PFASs, emerging PFASs including alternatives and precursors have been introduced to the industrial market. In this study, legacy and emerging PFASs were measured in seawater, sediment, and bivalves collected along the Korean coast to investigate the occurrence, distribution, contamination sources, and bioaccumulation potential of PFASs. Wide concentration ranges of legacy PFASs were detected in multiple environmental samples, indicating widespread contamination. C8-based PFASs (e.g., PFOA and PFOS) were still major contaminants in all of the environmental samples. Some precursors, such as 8:2 fluorotelomer sulfonate (8:2 FTS) and N-ethyl-perfluorooctane sulfonamidoacetic acid (N-EtFOSAA), and perfluoro-2-propoxypropanoic potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate (F-53B), an alternative to PFOS, were detected in sediment or bivalve samples, implying a shift in consumption patterns from legacy to emerging PFASs. The highest concentrations of PFASs in environmental samples were found at the locations near industrial complexes, such as those for the semi-conductor, paper mill, automobile, and metal-plating industry. This result indicates that PFAS contamination is associated with intensive industrial activities in the coastal environment. Matrix-dependent contamination and profiles of PFASs were observed. Seawater was dominated by short-chained PFASs as a prompt reflection of regulation, while the sediment and bivalves were dominated by long-chained PFASs. Carbon-chain length was a major factor governing environmental behavior and bioaccumulation of PFASs. This was the first nation-wide survey on legacy and emerging PFASs in the coastal environment of Korea.

Novel alternatives of perfluorooctane sulfonate (PFOS), chlorinated polyfluorinated ether sulfonates (Cl-PFAESs) are increasingly being detected in the aquatic and terrestrial environment. Previous studies mainly focused on aquatic biota; however, the knowledge about the ecotoxicological risk they pose to terrestrial plants was still lacking. In this study, the accumulation of two Cl-PFAES (6:2 and 8:2 Cl-PFAES) and PFOS in wheat seedlings at environmentally relevant levels (50 and 100 μg L−1) was investigated. Concentrations of Cl-PFAESs in the roots were an order of magnitude higher than those in shoots, indicating that they were primarily accumulated in the roots. The values of root and shoot bioconcentration factor was comparable between 6:2 Cl-PFAES and PFOS. However, these indexes of 8:2 Cl-PFAES were 42–91% higher and 70–76% lower than PFOS, respectively. As a result, 6:2 Cl-PFAES had a similar accumulation pattern as PFOS, whereas 8:2 Cl-PFAES was predominantly restricted to the roots, which might be attributed to their hydrophobicity and carbon chain length. In addition, at 250 mg L−1 of Cl-PFAESs, plant biomass and pigment content were 24–30% and 0.4–18%, respectively, which were lower than those of PFOS. As compared with PFOS, Cl-PFAESs induced higher levels of root membrane permeability, reactive oxygen species and malondialdehyde content, as well as reduced the activities of antioxidant enzymes and glutathione content. These suggested the occurrence of a severer oxidative damage and the breakdown of the antioxidant defence system in wheat cells. Therefore, we conclude that Cl-PFAESs might pose a higher potential threat to the environment than PFOS.

Per- and polyfluoroalkyl substances (PFASs) are contaminants of emerging concern (CECs) that cause concern regarding their environmental impact and risk to human health. In this study, zebrafish (Danio rerio) embryos were exposed to PFASs for six days, to investigate behaviour toxicity and bioconcentration factor (BCF). Nine individual PFASs (five C-4-C-8 perfluoroalkyl carboxylates (PFCAs) (PFPeA, PFHxA, PFHpA, PFOA, PFNA), three C-4, C-6 and C-8 perfluoroalkyl sulfonates (PFSAs) (PFBS, PFHxS, PFOS) and 6:2 fluorotelomersulfonate (6:2 FTSA)) and a mixture of these were investigated at seven concentrations ranging from environmentally relevant to acutely toxic levels. In exposed embryos, significant differences were found in total swimming distance (PFHpA, PFOA, PFNA, PFHxS, PFOS, 6:2 FTSA, PFAS mixture), burst activity (PFOA, PFNA, PFHxS, PFOS, PFAS mixture) and startle response (PFNA, PFHxS, PFOS, PFAS mixture). Toxicity was only observed at concentrations well above environmental levels. The toxicity of the PFAS mixture generally followed that of the individual substances, but the mixture reduced the potencies of individual PFASs. BCF was determined for all nine PFASs and ranged between 0.9 (PFPeA) and 2700 (PFOS). Long-chain PFASs (C-8) and PFASs with sulfonate as an active group showed the greatest toxic potential, while short-chain PFASs (C-6 and C-7) also caused significant behaviour alterations and accumulated in the embryos. To our knowledge, this is the first study to compare the behaviour toxicity of a PFAS mixture with that of the individual PFASs. Follow-up studies are needed to identify the mechanistic responses to PFAS mixtures. (C) 2019 Elsevier Ltd. All rights reserved.

[EN] The concerns about the undesired impacts on human health and the environment of long chain perfluorinated alkyl substances (PFASs) have driven industrial initiatives to replace PFASs by shorter chain fluorinated homologues. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) is applied as alternative to PFOS in metal plating and fluoropolymer manufacture. This study reports the electrochemical treatment of aqueous 6:2 FTSA solutions on microcrystalline BDD anodes. Bench scale batch experiments were performed, focused on assessing the effect of the electrolyte and the applied current density (5¿600 A m¿2) on the removal of 6:2 FTSA, the reduction of total organic carbon (TOC) and the fluoride release. Results showed that at the low range of applied current density (J¿=¿50 A m¿2), using NaCl, Na2SO4 and NaClO4, the electrolyte exerted a minimal effect on removal rates. The formation of toxic inorganic chlorine species such as ClO4¿ was not observed. When using Na2SO4 electrolyte, increasing the applied current density to 350¿600 A m¿2 promoted a notable enhancement of the 6:2 FTSA removal and defluorination rates, pointing to the positive contribution of electrogenerated secondary oxidants to the overall removal rate. 6:2 FTSA was transformed into shorter-chain PFCAs, and eventually into CO2 and fluoride, as TOC reduction was >90%. Finally, it was demonstrated that diffusion in the liquid phase was controlling the overall kinetic rate, although with moderate improvements due to secondary oxidants at very high current densities., Support from MINECO and SPAIN-FEDER 2014e2020 to project CTM 2016-75509-R and to the Spanish Excellence Network E3TECH (CTQ 2015-71650-RDT) is acknowledged. J. Carrillo-Abad thanks the Generalitat Valenciana for granting a post-doctoral fellowship (APOSTD/2015/019). The authors are thankful to Dr. R. Buck (Chemours Co.) for kindly providing samples of Capstone FS10

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 0.53-8.35 ng g-1 wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04-18.70 ng g-1 ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and C16 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.

This study assessed the aquatic toxicity and bioaccumulation potential of 6:2 fluorotelomer sulfonate (6:2 FTSA). Acute and chronic aquatic hazard endpoints indicate 6:2 FTSA is not classified for aquatic hazard according to GHS or European CLP legislation. The aqueous bioconcentration factors for 6:2 FTSA were40 and the dietary assimilation efficiency, growth corrected half-life and dietary biomagnification factor (BMF) were 0.435, 23.1d and 0.295, respectively. These data indicate that 6:2 FTSA is not bioaccumulative in aquatic organisms. Comparison of PNECs with the reported surface water concentrations (non-spill situations) suggests low risk to aquatic organisms from 6:2 FTSA. Future studies are needed to elucidate the biotic and abiotic fate of commercial AFFF surfactants in the environment.

The decomposition of perfluoroalkylether sulfonates C 2 F 5 OC 2 F 4 SO 3 - and C 3 F 7 OC 2 F 4 SO 3 - in subcritical water was investigated, and the results were compared with those for perfluorobutanesulfonate ( C 4 F 9 SO 3 - ), which has no ether linkage. This is the first report on the use of subcritical water to decompose perfluoroalkylether sulfonates, which are being developed as alternative surfactants to environmentally persistent and bioaccumulative perfluoroalkylsulfonates. Whereas C 4 F 9 SO 3 - showed little reactivity in subcritical water, C 2 F 5 OC 2 F 4 SO 3 - decomposed efficiently in subcritical water (∼350 °C) in the presence of oxygen gas to form F− and SO 4 2 - in the aqueous phase and CO2 in the gas phase as major products. Trifluoroacetic acid (CF3COOH, TFA) and trifluoromethane (CF3H) were also detected as minor products in the aqueous and gas phases, respectively. Similar decomposition behavior was observed for C 3 F 7 OC 2 F 4 SO 3 - , which decomposed at a rate that was somewhat higher than that of C 2 F 5 OC 2 F 4 SO 3 - . When argon was used in place of oxygen gas, the time profile of the decrease in the amount of C 2 F 5 OC 2 F 4 SO 3 - remained almost unchanged, but the product distribution changed markedly: the amounts of F−, SO 4 2 - , and CO2 dramatically decreased, the amounts of TFA and CF3H increased, and a new product, HCF 2 SO 3 - , was detected. These results clearly indicate that treatment with subcritical water in the presence of oxygen gas effectively mineralized perfluoroalkylether sulfonates to F−, SO 4 2 - , and CO2. On the basis of a product analysis, we propose a decomposition mechanism.

Worldwide environmental pollution by perfluorinated compounds (PFCs) has been reported. PFCs have also been reported to have nonpoint sources (NPSs). A fixed-point hourly monitoring in the river was conducted during a storm event using an automatic sampler to estimate the impact of the first-flush of PFCs from NPS in this study. Perfluorocarboxylates (PFCAs) and perfluoroalkyl sulfonates (PFASs) with different chain lengths were monitored. The concentrations of short- to medium-chain-length PFCAs such as PFHpA, PFOA and PFNA, and PFASs such as PFBS, PFPeS, PFHxS, PFHpS and PFOS showed no marked increase with the storm-runoff event. However, in contrast to this, concentrations of long-chain-length PFCAs such as PFDA and PFUnA increased markedly. The concentrations of PFDA and PFUnA increased 3.4 (1.5–5.0 ng L−1)- and 2.0 (3.3–6.7 ng L−1)-fold, respectively. This study demonstrates that large loads of long-chain-length PFCAs are discharged to the Hayabuchi River during the first-flush after the rain event.

A novel separation technique known as an aqueous surfactant two-phase (ASTP) extraction is a promising method to remove organic contaminants from wastewater. When cationic and anionic surfactants are mixed at certain surfactant concentrations and compositions, the solution separates into two immiscible aqueous phases. One is the surfactant-rich and the other is the surfactant-dilute phase. The organic contaminants will solubilize into the surfactant aggregates and concentrate in the small volume surfactant-rich phase. The other phase contains only small amount of surfactants and contaminants as the treated water. Most ASTP studies have used nonionic surfactants above the cloud point. Mixtures of anionic and cationic surfactants can also exhibit aqueous–aqueous phase separation and can be used in the ASTP extraction process. The phase behavior and performance of ASTP extraction using cationic surfactant dodecyltrimethylammonium bromide (DTAB) and anionic surfactant alkyldiphenyloxide di-sulfonate (DPDS) to extract benzene from wastewater was investigated in batch experiments. It was found that phase separation only occurs over a narrow range of molar ratios of DTAB:DPDS from 1.6:1 to 2.4:1. In this study, a 2:1 molar ratio of DTAB:DPDS at which there is no net charge in the surfactant aggregates show the highest extraction efficiency and lowest critical micelle concentration value with greatest synergism (highest negative values of the micellar interaction parameter). At a total surfactant concentration of 50 mM, the benzene partition ratio is 48 and 72% of the benzene is extracted into the surfactant-rich phase solution in a single stage extraction, which is superior performance compared to ASTP extraction using nonionic surfactants.

In the attempt to assess the relationship and interdependency among sediment toxic pollutants, in particular heavy metals, polycyclic aromatic hydrocarbons (PAH), and linear alkyl sulfonates (LAS) and some of the sediment typical components: inorganic carbon (IC), organic material (OM) and acid volatile sulphides (AVS), multivariate techniques of statistical analysis have been applied to a set of chemical data obtained by the analysis of the sediments of the Trasimeno Lake, a central Italy lake characterized by a large surface (128 km(2)) and a low mean depth (about 4.5 m). The results of principal component analysis (PCA) show interrelationships between: OM content and PAH, Pb, and Cu concentrations of the sediments, LAS and AVS, and AVS and IC. The effect of the different sampling periods on sediment composition and contamination level, and the clustering of the sampling sites as a consequence of pollutant load are also shown. The principal component bi-plot of the variables and samples indicates that PAH have the greatest influence on the separation of samples in the different sampling periods.

Certain perfluorinated chemicals (PFCs) in consumer products used indoors are potential indoor PFCs sources and have been associated with developmental toxicity and other adverse health effects in laboratory animals (Lao et al., 2007). The concentrations of selected PFCs including perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs), in 35 selected consumer products that are commonly used in indoors were measured from the year of 2007 through 2011. The products collected included carpet, commercial carpet-care liquids, household carpet/fabric-care liquids, treated apparel, treated home textiles, treated non-woven medical garments, floor waxes, food-contact paper, membranes for apparel, and thread-sealant tapes. They were purchased from retail outlets in the United States between March 2007 and September 2011. The perfluorocarboxylic acid (PFCA) contents in the products have shown an overall downward trend. However, PFOA (C8) could still be detected in many products that we analyzed. Reductions of PFCAs were shown in both short-chain PFCAs (sum of C4 to C7) and long-chain PFCAs (sum of C8 to C12) over the study period. There were no significant changes observed between short-chain PFCAs and long-chain PFCAs. Fourteen products were analyzed to determine the amounts of perfluoroalkyl sulfonates (PFASs) they contained. These limited data show the pronounced increase of perfluoro-butane sulfonate (PFBS), an alternative to perfluorooctanoic sulfonate (PFOS), in the samples. A longer and wider range of study will be required to confirm this observed trend.