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The development of efficient defluorination technology is an important issue because the kind of emerging pollutant of hexafluoropropylene oxide dimer acid (GenX) as an alternative to perfluorooctanoic acid (PFOA) has the higher environmental risks. In the UV/bisulfite system, we first developed a hydrophobic confined α-Fe 2 O 3 nanoparticle layer rich in oxygen vacancies, which accelerated the enrichment of HSO 3 - and GenX on the surface and pores through electrostatic attraction and hydrophobic interaction, retaining more hydrated electrons (e aq - ) and rapidly destroying GenX under UV excitation. Especially, under anaerobic and aerobic conditions, the degradation percentage of GenX obtain nearly 100%, defluorination of GenX to 88 and 57% respectively. It was amazed to find that the three parallel H/F exchange pathways triggered by the rapid reactions of e aq - and GenX, which were unique to anaerobic conditions, improved the efficiency of fluoride removal and weaken the interference of dissolved oxygen and H + . Therefore, this study provided an available material and mechanism for sustainable fluoride removal from wastewater in aerobic and anaerobic conditions.

The 6:2 fluorotelomer sulfonamide (6:2 FTSAm)-based compounds signify a prominent group of per- and polyfluoroalkyl substances (PFAS) widely used in contemporary aqueous film-forming foam (AFFF) formulations. Despite their widespread presence, the biotransformation behavior of these compounds in wastewater treatment plants remains uncertain. This study investigated the biotransformation of 6:2 FTSAm-based amine oxide (6:2 FTNO), alkylbetaine (6:2 FTAB), and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) in aerobic sludge over a 100-day incubation period. The biotransformation of 6:2 fluorotelomer sulfonamide alkylamine (6:2 FTAA), a primary intermediate product of 6:2 FTNO, was indirectly assessed. Their stability was ranked based on the estimated half-lives ( t 1/2 ): 6:2 FTAB (no obvious products were detected) ≫ 6:2 FTSA ( t 1/2 ≈28.8 days) > 6:2 FTAA ( t 1/2 ≈11.5 days) > 6:2 FTNO ( t 1/2 ≈1.2 days). Seven transformation products of 6:2 FTSA and 15 products of 6:2 FTNO were identified through nontarget and suspect screening using high-resolution mass spectrometry. The transformation pathways of 6:2 FTNO and 6:2 FTSA in aerobic sludge were proposed. Interestingly, 6:2 FTSAm was hardly hydrolyzed to 6:2 FTSA and further biotransformed to perfluoroalkyl carboxylic acids (PFCAs). Furthermore, the novel pathways for the generation of perfluoroheptanoic acid (PFHpA) from 6:2 FTSA were revealed.

High levels of 6:2 chlorinated polyfluorinated ether sulfonate (F-53B), which is a substitute for perfluorooctane sulfonate (PFOS), are detected in various environmental matrices, wildlife, and humans. Chlorinated polyfluorinated ether sulfonate has received increased attention due to its potential risk to ecosystems. However, its toxicity in the soil organisms remains unclear. In the present study, a comparative investigation was conducted on the toxicities of 6:2 Chlorinated polyfluorinated ether sulfonate (F-53B) and PFOS to the earthworm Eisenia. fetida. F-53B was significantly more acutely toxic to earthworms than PFOS, with median lethal concentrations of 1.43 and 1.83 mmol/kg dry soil (~816 and 984 mg/kg dry soil), respectively. Although both F-53B and PFOS, at 0.4 mmol/kg dry soil (=228 and 215 mg/kg dry soil) caused oxidative stress in earthworms, as evidenced by increased superoxide dismutase, peroxidase, and catalase activities as well as malondialdehyde level, the stress caused by F-53B was higher than that caused by PFOS. In transcriptomic and metabolomic studies, negative effects of PFOS and F-53B were observed on several metabolic processes in earthworms, including protein digestion and amino acid absorption, lipid metabolism, and the immune response. Compared with PFOS, F-53B exhibited a weaker disruption of lipid metabolism, comparable potency for toxicity to the immune response, and a stronger potency in extracellular matrix destruction along with apoptosis and ferroptosis induction. Hence, our data suggest that F-53B is more toxic than PFOS to earthworms. The findings provide some new insights into the potential toxicity of F-53B to soil organisms. Environ Toxicol Chem 2024;43:170-181. © 2023 SETAC., (© 2023 SETAC.)

The brick kilns in the South Asian region are widely documented to partially combust high-calorific waste components of synthetic-industrial origin, which contain hazardous constituents, including per- and polyfluoroalkyl substances (PFAS). Correspondingly, these establishments are necessarily built on agricultural land to easily acquire clay by excavating soil horizons, thus making cultivation soils vulnerable to PFAS contaminations. In this pioneering study, the occurrence, distribution profile, traceability and human health risk exposure to forty-four legacy and novel PFAS homologues, including two ultrashort-chain (C2-C3) PFAS, were investigated in agricultural soils around thirty-two conventional brick kilns across three districts of Pakistan. ⅀ 44 PFAS concentrations ranged from 14.3 to 465 ng/g (median: 28.2 ng/g), which were 2 to 70 folds higher than those in background soils, and slightly higher than those reported in agricultural soils in the global literature. The highest occurrence was observed for PFAS alternatives, i.e., 6:2 fluorotelomer sulfonate (6:2 FTSA) (40 %) and 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (4.5 %). A significant positive correlation (p < 0.01) was observed among the concentrations of short-chain perfluoroalkyl acids (C4-C7) and novel PFOS substitutes, implying their origin from common sources. Furthermore, ultrashort-chain and short-chain perfluorocarboxylic acids (PFCA) (89 %) and perfluorosulfonic acids (PFSA) (63 %) dominated over long-chain's PFCA (11 %) and PFSA (37 %), respectively. The estimated daily intake to children exposed in surrounding inhabited communities, at 95th percentile concentrations was found to be approaching the European tolerable daily intake limit of 0.63 ng/kg bw/day. Therefore, the brick manufacturing industry is identified as a novel source of PFAS in the adjacent environment and for residents. This suggests the need for further investigations to elucidate the origin of emerging contaminants in the waste streams of the region to safeguard ecological integrity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Wastewater treatment plants (WWTPs) are typical point sources of per- and polyfluoroalkyl substances (PFAS) released into the environment. The suspect and nontarget screening based on gas chromatography or liquid chromatography-high resolution mass spectrometry were performed on atmosphere, wastewater, and sludge samples collected from two WWTPs in Tianjin to discover emerging PFAS and their fate in this study. A total of 40 PFAS (14 neutral and 26 ionic) and 64 PFAS were identified in the atmosphere and wastewater/sludge, respectively, among which 5 short-chain perfluoroalkyl sulfonamide derivatives, 4 ionic PFAS, and 15 aqueous film-forming foam-related cationic or zwitterionic PFAS have rarely or never been reported in WWTPs in China. Active air sampling is more conducive to the enrichment of emerging PFAS, while passive sampling is inclined to leave out some ultrashort-chain PFAS or unstable transformation intermediates. Moreover, most precursors and intermediates could be enriched in the atmosphere at night, while the PFAS associated with aerosols with high water content or particles enter the atmosphere easily during the day. Although most emerging PFAS could not be eliminated efficiently in conventional treatment units, deep bed filtration and advanced oxidation processes could partly remove some emerging precursors.

Oil refinery activity can be an emission source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, while the contamination profiles in soils remain unknown. This study investigated 44 target PFAS in soil samples collected from an oil refinery in Southeastern China, identified novel PFAS, and characterized their behaviors by assessing their changes before and after employing advanced oxidation using a combination of nontarget analysis and a total oxidizable precursor (TOP) assay. Thirty-four target PFAS were detected in soil samples. Trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were the dominant PFAS. Twenty-three novel PFAS of 14 classes were identified, including 8 precursors, 11 products, and 4 stable PFAS characterized by the TOP assay. Particularly, three per-/polyfluorinated alcohols were identified for the first time, and hexafluoroisopropanol (HFIP) quantified up to 657 ng/g dw is a novel precursor for TFA. Bistriflimide (NTf2) potentially associated with an oil refinery was also reported for the first time in the soil samples. This study highlighted the advantage of embedding the TOP assay in nontarget analysis to reveal not only the presence of unknown PFAS but also their roles in environmental processes. Overall, this approach provides an efficient way to uncover contamination profiles of PFAS especially in source-impacted areas.

Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl 3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe 3+ as an oxidizing agent from self-sacrificial Fe 3 O 4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe 3+ , PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Emerging alternatives to perfluorooctane sulfonate (PFOS), including 6:2 chlorinated polyfluorinated ether sulfonate (F-53B) and p-perfluorous nonenoxybenzene sulfonate (OBS), have been widely detected in the real environment as PFOS restriction. However, the toxicity in plants and the underlying mechanism of F-53B and OBS remain scarce, especially compared to PFOS. PFOS and their emerging alternatives pose significant potential risks to food, especially for crops, safety and human health with the great convenience of high chemical stability. Germination toxicity, oxidative stress biomarkers, and metabolomics were used to compare the relative magnitudes of toxicity of PFOS and its alternatives in wheat (Triticum aestivum L.). PFOS, F-53B, and OBS inhibited wheat germination compared to the control group, with germination inhibition rates of 45.6%, 53.5%, and 64.3% at 400 μM PFOS, F-53B, and OBS exposure, respectively. Moreover, oxidative stress biomarker changes were observed in PFOS, F-53B, and OBS, with OBS being more pronounced. The chlorophyll concentrations in wheat shoots increased, and the anthocyanin concentration decreased along with the increased exposure concentration. Superoxide dismutase (SOD) activity increased in wheat root but decreased in the shoot. Peroxidase (POD) activity and malondialdehyde (MDA) concentration increased, whereas catalase (CAT) activity decreased. Regarding metabolomics, PFOS, F-53B, and OBS exposure (10 μM) significantly altered 85, 133, and 134 metabolites, respectively. According to KEGG enrichment analysis, F-53B specifically affects lipid metabolism, whereas OBS causes an imbalance in amino acid and carbohydrate metabolism. These findings suggested that PFOS, F-53B, and OBS have distinct toxic mechanisms. Thus, our results indicated that the relative size of the toxicity in wheat is as follows: OBS > F-53B > PFOS, and this finding provides a new reference basis for the phytotoxicity assessment of F-53B and OBS., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) have received increasing scientific and regulatory attention due to their global distribution and health hazards. However, little is known about the PFAS composition of fluorinated products commercially available in China. In this study, a sensitive and robust analytical method was proposed for the comprehensive characterization of PFAS in aqueous film-forming foam and fluorocarbon surfactants in the domestic market based on liquid chromatography-high resolution mass spectrometry in full scan acquisition mode followed by parallel reaction monitoring mode. Consequently, a total of 102 PFAS from 59 classes were elucidated, of which 35 classes are reported for the first time, including 27 classes of anionic, seven classes of zwitterionic, and one class of cationic PFAS. The anionic-type products are mainly C6 fluorotelomerization-based (FT-based) PFAS. Perfluorooctanoic acid and perfluorooctane sulfonate are negligible, while some known electrochemical fluorination-based long-chain precursors in zwitterionic products are worthy of concern because of their high abundance and potential degradation. New precursors detected in zwitterionic products are FT-based PFAS, for example, 6:2 FTSAPr-AHOE and 6:2 FTSAPr-diMeAmPrC. The structural elucidation of PFAS in commercial products facilitates a better assessment of human exposure and environmental release., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Electrochemical oxidation (EO) has been shown to have the unique ability to degrade perfluorooctanoic acid (PFOA), although the radical chemistry involved in this degradation is unclear, particularly in the presence of chloride ions (Cl - ). In this study, reaction kinetics, free radical quenching, electron spin resonance, and radical probes were used to examine the roles of ·OH and reactive chlorine species (RCS, including Cl·, Cl 2 •- , and ClO·) in the EO of PFOA. Using EO in the presence of NaCl, PFOA degradation rates of 89.4%-94.9% and defluorination rates of 38.7%-44.1% were achieved after 480 min with PFOA concentrations ranging from 2.4 to 240 μM. The degradation occurred via the synergistic effect of ·OH and Cl· rather than through direct anodic oxidation. The degradation products and density functional theory (DFT) calculations revealed that Cl· triggered the first step of the reaction, thus the initial direct electron transfer was not the rate-limiting step of PFOA degradation. The change in Gibbs free energy of the reaction caused by Cl· was 65.57 kJ mol -1 , which was more than two times lower than that triggered by ·OH. However, ·OH was involved in the subsequent degradation of PFOA. The synergistic effect of Cl· and ·OH in PFOA degradation is demonstrated for the first time in this study, which is promising for the development of electrochemical technology to remove perfluorinated alkyl substances from the environment.

Occupational exposure to per- and polyfluoroalkyl substances (PFASs) is of serious concern because their adverse health effects. Nevertheless, knowledge regarding contamination in e-waste dismantling regions is rather scarce. We therefore analysed seven neutral PFASs (n-PFASs) and forty ionized PFASs (i-PFASs) in dust and hand wipes collected from an e-waste dismantling plant and homes. Both dust (1370 ng/g) and workers' hand wipe (1100 ng/m 2 ) in e-waste dismantling workshops contained significantly higher median levels of ∑PFASs than those from homes (684 ng/g and 444 ng/m 2 ) (p < 0.01). ∑PFAS concentrations in dust and on workers' hand wipes from workshops were significantly higher than those from storage area. 8:2 fluorotelomer alcohol was the dominant n-PFAS in workshop dust (70.7%) and on worker's hand wipes (46.6%). Perfluoroalkyl carboxylic acids (C2 -C3) were the significant components (based on concentration) of i-PFASs in dust (57.9%) and on hand wipes (89.6%). A significant positive correlation (p < 0.001) of ∑PFAS concentrations between workshop dust and workers' hand wipes was observed, indicating that they come from common sources. Compared to dust ingestion, hand-to-mouth contact was highlighted as a vital exposure route, accounting for 68.8% for workers and 72.2% for residential population, respectively, of the sum of two exposure doses., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

As alternatives of long-chain PFASs (Poly- and perfluoroalkyl substances), perfluoroalkyl phosphinic acids (PFPiAs) are increasingly observed in the environment, but their environmental behaviors have not been well understood. Here, the microbial biotransformation of C6/C6 and C8/C8 PFPiA in two soils (Soil N and Y) was investigated. After 252 d and 330 d of incubation with PFPiAs in Soil N and Y respectively, the levels of PFPiAs decreased distinctly, accompanied by the increasing perfluorohexaphosphonic acid (PFHxPA) or perfluorooctanophosphonic acid (PFOPA) formation, magnifying PFPiAs were susceptible to C-P cleavage, which was also confirmed by the density functional theory calculations. The half-lives of the PFPiAs were longer than one year, while generally shorter in Soil N than in Soil Y and that of C6/C6 was shorter than C8/C8 PFPiA (392 d and 746 d in Soil N, and 603 and 1155 d in Soil Y, respectively). Metagenomic sequencing analysis revealed that Proteobacteria as the primary host of the potential functional genes related to CP bond cleavage might be the crucial phyla contributing to the biotransformation of PFPiAs. Meanwhile, the more intensive interactions between the microbes in Soil N consistently contribute to its greater capacity for transforming PFPiAs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Per- and polyfluoroalkyl substances (PFASs) have garnered attention globally given their ubiquitous occurrence, toxicity, bioaccumulative potential, and environmental persistence. Sorption is widely used to remove PFASs given its simplicity and cost-effectiveness. This article reviews recently fabricated sorbents, including carbon materials, minerals, polymers, and composite materials. The characteristics and interactions of the sorbents with PFASs are discussed to better understand sorptive processes. Various sorbents have exhibited high removal rates for legacy perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Novel polymers with special design better remove long- and short-chain PFASs than other sorbents. Although hydrophobic and electrostatic interactions mainly drive the sorption of anionic, cationic, and zwitterionic PFASs, enhancing PFAS sorption on designed sorbents has mainly depended on improving electrostatic interactions. Pearson correlation analysis showed that PFOS sorption capacity of sorbents is positively correlated with their specific surface area. Newly discovered pathways, including the air-water interfacial adsorption, F-F fluorophilic interactions, and (hemi) micelle formation, can enhance PFAS sorption to a certain extent. In addition to PFOA and PFOS, the sorption of emerging PFASs, including aqueous film-forming foam-relevant PFASs, constitutes a new research direction. The functionalization methods for enhancing PFAS sorption and challenges of PFAS sorption are also discussed to provide scope for future research. The discussions herein may contribute to developing efficient sorption technologies to remove PFASs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Limited information is available about prenatal exposure to per- and polyfluoroalkyl substances (PFAS) in electronic waste (e-waste) recycling sites. In this study, we determined 21 emerging PFAS and 13 legacy PFAS in 94 paired maternal and cord serum samples collected from an e-waste dismantling site in Southern China. We found 6:2 fluorotelomer sulfonate (6:2 FTSA), 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), and perfluorooctanephosphonate (PFOPA) as the major emerging PFAS, regardless of matrices, at median concentrations of 2.40, 1.78, and 0.69 ng/mL, respectively, in maternal serum samples, and 2.30, 0.73, and 0.72 ng/mL, respectively, in cord serum samples. Our results provide evidence that e-waste dismantling activities contribute to human exposure to 6:2 FTSA, 6:2 Cl-PFESA, and PFOPA. The trans-placental transfer efficiencies of emerging PFAS (0.42-0.94) were higher than that of perfluorooctanesulfonic acid (0.37) and were structure-dependent. The substitution of fluorine with chlorine or hydrogen and/or hydrophilic functional groups may alter trans-placental transfer efficiencies. Multiple linear regression analysis indicated significant associations between maternal serum concentrations of emerging PFAS and maternal clinical parameters, especially liver function and erythrocyte-related biomarkers. This study provides new insights into prenatal exposure to multiple PFAS in e-waste dismantling areas and the prevalence of emerging PFAS in people living near the sites.

Per- and polyfluoroalkyl substances (PFASs) are applied in oil exploitation activity. In this study, non-target and suspect target analyses with high-resolution mass spectrometry were used for identification of novel PFASs in the oilfield environment. A total of thirty-seven PFAS homologues belonging to eight classes were identified as level 4 or above, which partly explained the amount of potential unknown PFAS-precursors that were indicated by total oxidisable precursor assay in our previous study. Hydrogen-substituted and ether-substituted homologues were the main identified PFASs, and seven of them were newly reported homologues. C1-C3 perfluoroalkane sulphonic acids (PFSAs) were also for the first time identified in the oilfield. The sediment-water partitioning coefficients of most identified PFAS homologues positively correlate with their predicted octanol-water partitioning coefficients while those of C1-C3 PFSAs may have elevated sediment partitioning potential as also previously observed for ultra-short chain C2-C3 perfluoroalkyl carboxylic acids. The crude oil and sludge samples were further examined with the target and identified PFAS profiles. An annual flux of 10.4 kg/y via oil production was estimated in Dagang Oilfield with 16.6 % not from the target PFASs. This demonstrates that oil exploitation activities can be a significant underlying source of PFASs to the environment., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Fluorotelomer alcohols (FTOHs) are a kind of volatile monomers that can be released from FTOH-based products and their ubiquitous occurrence raises concerns for their plant uptake. To study plant uptake pathway, translocation, and transformation characteristics of 8:2 FTOH, ryegrass (Lolium perenne L.) was selected as a model plant for 8:2 FTOH exposure via air and/or soil uptake for 4 weeks in custom-built closed exposure chambers. The bio-degradation of spiked 8:2 FTOH in the soil led to the production of C6-C8 perfluoroalkyl carboxylic acids (PFCAs) and other intermediates, and perfluorooctanoic acid (PFOA) was the main product (54.9%-88.9%). In the ryegrass, foliar uptake of 8:2 FTOH contributed 78.1% ± 3.4% to the total shoot accumulation while PFOA in shoot was mainly from root uptake of PFOA and the further biotransformation of other unmonitored intermediates biodegraded from 8:2 FTOH in the soil (83.7% ± 7.3%). The results in this study provides the first laboratory evidences that foliar uptake of airborne 8:2 FTOH can be a major pathway over root uptake and its subsequent biotransformation contribute to the burden of PFCA accumulation in plants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Perfluoroalkyl sulfonates (PFSAs), perfluoroalkyl carboxylates (PFCAs), and emerging alternatives and precursors of these compounds were determined in tissues of finless porpoise ( Neophocaena asiaeorientalis sunameri ) collected from East China Sea in 2009-2010 and 2018-2019. The median hepatic concentrations of emerging poly- and perfluoroalkyl substances (PFASs), including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA), 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA), and 4,8-dioxa-3 H -perfluorononanoate (ADONA) were 16.2, 2.16, < LOQ (limit of quantification) and < LOQ ng/g ww (wet weight), respectively. The concentrations of legacy substances, perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA), were 86.9 and 1.95 ng/g ww, respectively. The liver concentrations of 6:2 Cl-PFESA, HFPO-DA, and perfluorohexanesulfonate (PFHxS) increased with time between 2009-2010 and 2018-2019. Further, concentrations of PFOA showed a declining trend in finless porpoise, whereas PFOS and its precursor (i.e., perfluorooctane sulfonamide [FOSA]) showed an increasing trend with time between 2009-2010 and 2018-2019. Analysis of PFASs in nine different tissues/organs of finless porpoise (i.e., liver, heart, intestine, spleen, kidney, stomach, lung, muscle, and skin) revealed a similar distribution pattern between 6:2 Cl-PFESA and PFOS; however, the tissue distribution patterns differed between HFPO-DA and PFOA. The concentrations of PFAS alternatives in kidney were similar or lower than the prototype compounds PFOS and PFOA (i.e., 8:2 Cl-PFESA < 6:2 Cl-PFESA ≈ PFOS; HFPO-DA < PFOA), implying slow renal excretion of PFAS alternatives as that of legacy PFASs. The estimates of body burdens of PFASs in porpoises suggested comparable accumulation of PFAS alternatives and legacy PFSAs and PFCAs. This study provides novel information on temporal trends and tissue distribution of emerging PFASs in marine mammals in China.

Per- and polyfluoroalkyl substances (PFASs) were analyzed in outdoor ( n = 101) and indoor dust ( n = 43, 38 paired with outdoors) samples across mainland China. From 2013 to 2017, the median concentration of ∑PFASs in outdoor dust tripled from 63 to 164 ng/g with an elevated contribution of trifluoroacetic acid and 6:2 fluorotelomer alcohol. In 2017, the indoor dust levels of ∑PFASs were in the range 185-913 ng/g, which were generally higher than the outdoor dust levels (105-321 ng/g). Emerging PFASs were found at high median levels of 5.7-97 ng/g in both indoor and outdoor dust samples. As first revealed by the total oxidized precursors assay, unknown perfluoroalkyl acid (PFAA)-precursors contributed 37-67 mol % to the PFAS profiles in indoor dust samples. A great proportion of C8 PFAA-precursors were precursors for perfluorooctanesulfonic acid, while C6 and C4 PFAA-precursors were mostly fluorotelomer based. Furthermore, daily perfluorooctanoic acid (PFOA) equivalent intakes of PFAAs (C4-C12) mixtures via indoor dust were first estimated at 1.3-1.5 ng/kg b.w./d for toddlers at high scenarios, which exceeds the derived daily threshold of 0.63 ng/kg b.w./d. from the European Food Safety Authority (EFSA). On this basis, an underestimation of 56%-69% likely remains without considering potential risks due to the biotransformation of unknown PFAA-precursors.

Per- and polyfluoroalkyl substances (PFAS) are a family of anthropogenic chemicals, that have attracted increasing attention since the early 2000 s. Although forests have been shown to act as a filter and important sink for nonpolar persistent organic pollutants (POPs), relevant reports on PFAS are lacking. Air, soil, and leaf samples were collected inside and outside the forest from two regions of the Three-North Shelter Forest in northern China between 2017 and 2018. Twenty-seven PFAS were analyzed to study the effect of forest on the transport and fate of PFAS. The average ratios of PFAS in the air outside to inside the forest (Q air ) ranged from 2.83 ± 0.78-10.6 ± 3.1. A significant positive correlation was found between Q air and the n-octanol-air partition coefficient of individual PFAS (p = 0.041). Higher Q air values for most ionic PFAS were found in broad-leaved forests than in coniferous forests. Soil samples outside the forests showed higher PFAS levels than those inside. The measured concentrations of 8:2 fluorotelomer alcohol, a volatile neutral PFAS, in leaf samples were two orders of magnitude higher than those estimated using the equilibrium leaf-air partition of nonpolar POPs, indicating that it may not fit the case of PFAS with surface activity., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Advanced reduction by strong reducing hydrated electrons is a promising approach to degrade per- and polyfluoroalkyl substances (PFAS). This research aimed to investigate the effectiveness of UV/Iodide system for 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA, F-53B) degradation in aqueous solutions. Results from this work demonstrated that UV irradiation with an addition of 0.3 mM KI resulted in 55.99% degradation of F-53B within 15 min and almost 100% within 2 h. The defluorination efficiency of F-53B in the UV/Iodide system was 2.6 times higher than that in the sole UV system after 2 h of irradiation. The degradation efficiency of F-53B was not significantly affected by air purging. The defluorination efficiency with air bubbling, however, was 14.57% lower than that with nitrogen purging. The photodegradation of F-53B in the UV/Iodide system could be well described by a pseudo-first-order kinetic model. Degradation rate constant of F-53B correlated positively with the initial concentration. At 20 μg/L, the pseudo-first-order rate constant was 5.641 × 10 -2 min -1 and the half-life was 12.29 min. Higher initial concentration also required less energy input to achieve the same degradation efficiency. The detection and identification of degradation intermediates implied that destruction of F-53B started from dechlorination and followed by continuously "flaking off" CF 2 units., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The dust on indoor and outdoor surfaces of the window glasses were collected using sterile cotton balls in 11 cities from China. Two sampling campaigns were conducted with the time interval of 7 days to investigate the accumulation especially during the Spring festival holidays. Twenty-nine perfluoroalkyl acids (PFAA) were quantified to investigate concentration, composition, and toddlers' exposure. The concentrations of ∑PFAA ranged from no detection (nd) to 43 ng/m 2 (mean 8.9 ± 10 ng/m 2 ). Perfluorobutanoic acid (PFBA) was detected in 78% samples and accounted for 55 ± 21% of ∑PFAA concentrations. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were detected in more than 50% samples indicating the use of alternatives. Fluorotelomer carboxylic acid (FTCA) and fluorotelomer unsaturated acid (FTUCA) were found in the dust, implying the degradation of fluorotelomer alcohols (FTOH). The highest concentration of ∑PFAA (43 ng/m 2 ) was found in outdoor dust from Xinzhou, Shanxi Province. Higher ∑PFAA concentrations were found in indoor dust than outdoor in 6 paired samples (3 from Feb. 14 and 3 from Feb. 21). In Tianjin and Handan, the concentrations of ∑PFAA from outdoor surfaces were higher in sampling campaign I (SC I, Feb. 21) than in sampling campaign II (SC II, Feb. 14), implying intensive outdoor release. The exposure of 2-year-old toddlers to PFAA via hand-to-mouth ingestion and dermal absorption was estimated; the mean values of intake were 2.1 and 1.5 pg/kg body weight, respectively, assuming an exposure time of 1 h., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Polyfluoroalkyl phosphoric acid diesters (diPAPs) have been widely and increasingly detected in various environmental mediums. The degradation of diPAPs brings perfluoroalkyl carboxylic acids (PFCAs) concerned of adverse health effects. DiPAPs mainly occur in particulate matter in ambient air and their photo-degradation behaviors have not been investigated. In this study, heterogeneous photo-degradation of 6:2 diPAP was studied on four model mineral components in ambient dust. 6:2 diPAP was found to undergo a fast degradation on titanium dioxide (TiO 2 ) particles as well as on artificial mineral dust containing TiO 2 (2.67% in mass) to produce C5-C7 PFCAs and other intermediates. Based on monitored intermediates and further degradation tests on important intermediates, thermodynamic calculation of energy barrier and Gibbs Free Energy was used to explain the observed degradation patterns and accordingly the degradation pathways of diPAPs were proposed. The increase in relative humidity promotes the production of hydroxyl radicals, which enhances the hydrolysis of 6:2 mono- and di-PAPs and the yield of C5 and C7 PFCAs. Oxygen is critical for radical formation, which bypasses the production of fluorotelomer carboxylic acid. Results of this study for the first time demonstrate that diPAP may account for additional PFCA sources in both indoor and outdoor environments and the heterogeneous degradation pathways were different from those of volatile fluorotelomer alcohols., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Per-/polyfluoroalkyl substances (PFASs), as a group of synthetic chemicals, have been extensively detected in human samples. Recently, epidemiological investigations have reported relationships between exposure to PFASs with risk of type 2 diabetes mellitus (T2DM), but with contradictory results. In this study, a case-control study was conducted to explore associations between serum PFASs and T2DM risk among 252 T2DM cases and 252 controls, who were both diagnosed according to fasting glucose and glycosylated hemoglobin levels. Besides, dose-response relationships were analyzed to clarify effects of PFAS exposure on T2DM risk at different exposure levels. Multivariable logistic regression models showed that compared to the lowest tertiles, elevated odds of T2DM risk were observed in the middle tertiles of perfluorohexane sulfonic acid (PFHxS) [odds ratio (OR): 4.09; 95% confidence interval (CI): 2.23, 7.50; p < 0.01] and perfluorohexane sulfonic acid (PFHpA) (OR: 1.87; 95% CI: 1.06, 3.29; p = 0.03), but not in the highest tertiles, and the restricted cubic spline regression models presented inverted U-shaped dose-response relationships for exposure to PFHxS and PFHpA with T2DM risk, indicating non-monotonic dose-response effect and low-dose effect. Most other PFASs were inversely associated with risk of T2DM, especially at higher exposure levels. Our findings suggested that there are associations between exposure to PFASs and risk of T2DM. Further mechanism research is worthy to be conducted to elucidate the mode of action of different PFASs on T2DM at different exposure levels., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

Per- and polyfluoroalkyl substances (PFASs) are environmentally and biologically persistent anthropogenic chemicals linked to adverse health outcomes. Epidemiological data have revealed association between exposure to specific PFAS and disruption of insulin level in bodies. However, the effect of PFASs on insulin secretion and the responsible molecular mechanism are poorly understood. In the present study, we used perfluorooctane sulfonate (PFOS) as a representative PFAS family member to investigate its effect on the insulin secretion in mouse pancreatic β cells (β-TC-6). Our results showed that exposure to PFOS inhibited silent information regulator 1 (SIRT1) activity, and molecular simulation showed PFOS could fit into the pocket overlapped with the nicotinamide adenine dinucleotide (NAD + ) binding cavity in SIRT1. PFOS exposure upregulated uncoupling protein 2 (UCP2) expression, and this upregulation was blunted in the presence of Ex-527, a SIRT1 specific inhibitor. The mitochondria membrane potential (ΔΨm), as well as the glucose-induced ATP production and Ca 2+ influx decreased under PFOS treatment. PFOS continual exposure (48 h) impaired glucose stimulated insulin secretion (GSIS), while the gene expression of insulin was not significantly altered. Importantly, the SIRT1 activator and UCP2 inhibitor could partly reverse the PFOS-induced impairment of GSIS. Taken together, the results suggested that PFOS continual exposure could inhibit SIRT1 activity, and the SIRT1-UCP2 pathway mediated, at least partially, the PFOS induced GSIS impairment., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Skiing is an important direct input route of per- and polyfluoroalkyl substances (PFASs) to the environment. However, there has been no study on the occurrence of PFASs in Chinese ski area. In this study, 27 neutral PFASs (n-PFASs) and ionic PFASs (i-PFASs), including 4 emerging PFASs, were analyzed in the multimedia samples collected from areas around six ski resorts in Zhangjiakou and Shenyang to investigate the occurrence and seasonal distribution of PFASs. Both i-PFASs and n-PFASs were found in the air (13.2 ± 9.5 pg/m 3 and 167 ± 173 pg/m 3 , respectively) and pine needles [1.44 ± 0.96 ng/g dry weight (dw) and 0.983 ± 0.590 ng/g dw], whereas only i-PFASs were found in the soil (0.755 ± 0.281 ng/g dw) and snow (3.30 ± 2.66 ng/kg). i-PFASs were significantly higher in samples collected around ski resorts than those from rural sites (n = 105, p < 0.05). Significantly higher perfluorooctanoate concentrations were found in the air around the ski resorts in winter (n = 33, p < 0.05). The i-PFASs were stable in the needle, and the short-chain PFASs in the needle could be ascribed to both air and root uptake. More attention should be paid to PFASs emissions in Zhangjiakou with the approaching 2022 Winter Olympic Games., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The co-contamination by perfluoroalkyl acids (PFAAs) and heavy metals (HMs) is ubiquitous in the surface environment subjected to sewage irrigation and land application of sludge. However, the joint effects of HMs and PFAAs on plant roots are not well clarified. This study explored the root uptake and acropetal translocation behaviors of C2-C8 PFAAs by wheat (Triticum acstivnm L.) under the co-exposure of copper (Cu). The underlying uptake mechanisms of PFAAs were verified in a defective root system. The results showed that excessive Cu (100-400 μmol/L) damaged the cell membrane of wheat root to increase electrolytic leakage. In the defective root system, the root concentrations of PFAAs decreased by 6%-73% and the decrease rates were negatively associated with the carbon chain length of PFAAs. Along with the decrease in root concentrations of PFAAs, the amount of ultrashort-chain (C2-C3) and short-chain (C4-C6) PFAAs translocated to the shoot also decreased by 45%-84%. In contrast, the acropetal translocation of long-chain (C8) PFAAs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), was enhanced under Cu exposure due to the increase in root permeability as observed by increased electrolytic leakage. The shoot concentrations of PFOA and PFOS under Cu exposure were up to 5.5 and 11 times higher than those in the control, respectively. These results suggested that PFOA and PFOS could enter wheat root more easily through the breaks caused by Cu exposure and thereby their acropetal transportation to shoot was enhanced. Therefore, the risk of plant accumulation of long-chain PFAAs can be potentially underestimated if without considering the co-contamination with HMs in the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Tianjin, located in Bohai Bay, China, constitutes a relevant study area to investigate emerging per- and polyfluoroalkyl substances (PFASs) due to its high population density, clustering of chemical and aircraft industries, as well as international airports, harbors, and oil rigs. In this study, 53 anionic, zwitterionic, and cationic PFASs were monitored in river surface water, groundwater, seawater, and sediments in this area (overall n = 226). 6:2 chlorinated polyfluorinated ether sulfonic acid (Cl-PFESA), perfluorooctanoic acid, and perfluorooctane sulfonic acid were generally the predominant PFASs. 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB) was also widespread (occurrence >86%), with the highest concentration (1300 ng/L) detected at contamination hot spots impacted by wastewater effluents. The aqueous film-forming foam (AFFF)-related PFASs with sulfonamide betaine, amine oxide, amine, or quaternary ammonium moieties are also reported for the first time in river water and seawater samples. Fifteen classes of infrequently reported PFASs, including n :2 FTABs and n :2 fluorotelomer sulfonamide amines, hydrogen-substituted PFESA homologues, and p -perfluorous nonenoxybenzenesulfonate (OBS), were also identified in the water and sediment samples using suspect screening. Field-derived sediment-water distribution coefficients ( K d ) of these emerging PFASs are provided for the first time, confirming that cationic and zwitterionic PFASs tend to be strongly associated with sediments.

Per- and polyfluoroalkyl substances (PFASs) contamination in the Bohai Sea and its surrounding rivers has attracted considerable attention in recent years. However, few studies have been conducted regarding the distribution of PFASs in multiple environmental media and their distributions between the suspended particles and dissolved phases. In this study, surface water, surface sediment, and air samples were collected at the Bohai Sea to investigate the concentration and distribution of 39 targeted PFASs. Moreover, river water samples from 35 river estuaries were collected to estimate PFAS discharge fluxes to the Bohai Sea. The results showed that total ionic compound (Σi-PFASs) concentrations ranged from 19.3 to 967 ng/L (mean 125 ± 152 ng/L) in the water and 0.70-4.13 ng/g dw (1.78 ± 0.76 ng/g) in surface sediment of the Bohai Sea, respectively. In the estuaries, Σi-PFAS concentrations were ranged from 10.5 to 13500 ng/L (882 ± 2410 ng/L). In the air, ΣPFAS (Σi-PFASs + Σn-PFASs) concentrations ranged from 199 to 678 pg/m 3 (462 ± 166 pg/m 3 ). Perfluorooctanoic acid (PFOA) was the predominant compound in the seawater, sediment, and river water; in the air, 8:2 fluorotelomer alcohol was predominant. Xiaoqing River discharged the largest Σi-PFAS flux to the Bohai Sea, which was estimated as 12,100 kg/y. Some alternatives, i.e., 6:2 fluorotelomer sulfonate acid (6:2 FTSA), hexafluoropropylene oxide dimer acid (HFPO-DA), and chlorinated 6:2 polyfluorinated ether sulfonic acid (Cl-6:2 PFESA), showed higher levels than or comparable concentrations to those of the C8 legacy PFASs in some sampling sites. The particle-derived distribution coefficient in seawater was higher than that in the river water. Using high resolution mass spectrometry, 29 nontarget emerging PFASs were found in 3 river water and 3 seawater samples. Further studies should be conducted to clarify the sources and ecotoxicological effects of these emerging PFASs in the Bohai Sea area., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The occurrence of legacy and novel per- and polyfluoroalkyl substances (PFASs) in multiple matrices from a farmland environment was investigated in the Beijing-Tianjin-Hebei core area of northern China. PFASs were ubiquitously detected in farmland soils, and the detection frequency of 6:2 chlorinated polyfluoroalkyl ether sulfonic acid (6:2 Cl-PFESA) was higher than that of perfluorooctane sulfonic acid (98% vs. 83%). Long-chain PFASs, including 6:2 Cl-PFESA, showed a centered distribution pattern around the metropolis of Tianjin, probably due to the local intensive industrial activity, while trifluoroacetic acid (TFA) showed a decreasing trend from the coast to the inland area. Other than soil, TFA was also found at higher levels than other longer-chain PFASs in dust, maize (Zea mays), poplar (Populus alba) leaf and locust (Locusta migratoria manilens) samples. Both poplar leaves and locusts can be used as promising biomonitoring targets for PFASs in farmland environments, and their accumulation potential corresponds with protein and lipid contents. Apart from being exposed to PFASs via food intake, locusts were likely exposed via uptake from soil and precipitated dust in farmland environments. The biomonitoring of locusts may be more relevant to insectivores, which is important to conducting a comprehensive ecological risk assessment of farmland environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

With the phase out of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), the composition profiles of poly- and perfluoroalkyl substance (PFAS) in our living environment are unclear. In this study, 25 PFASs were analyzed in indoor dust samples collected from urban, industrial, and e-waste dismantling areas in China. PFOS alternatives, including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (median: 5.52 ng/g) and 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA) (1.81 ng/g), were frequently detected. By contrast, PFOA alternatives, such as hexafluoropropylene oxide dimer acid (HPFO-DA, Gen-X) and ammonium 4,8-dioxa-3H-perfluorononanoate (ADONA), were not found in any of the dust samples. As expected, all legacy PFASs were widely observed in indoor dust, and 4 PFAS precursors were also detected. Dust concentrations of 6:2 Cl-PFESA were strongly correlated (p < 0.05) with those of 8:2 Cl-PFESA regardless of sampling sites. 6:2 Cl-PFESA was also significantly associated with that of PFOS in industrial and e-waste (p < 0.01) areas. Association analysis suggested that the sources of PFOS and its alternatives are common or related. Although ∑Cl-PFESA concentration was lower than that of PFOS (17.4 ng/g), industrial areas had the highest 6:2 Cl-PFESA/PFOS ratio (0.63). Composition profiles of PFASs in the industrial area showed the forefront of fluorine change. Thus, the present findings suggested that Cl-PFESAs are widely used as PFOS alternatives in China, and high levels of human Cl-PFESA exposure are expected in the future. Short-chain PFASs (C4-C7) were the predominant PFASs found in dust samples, contributing to over 40% of ∑total PFASs. Furthermore, perfluoro-1-butanesulfonate/PFOS and perfluoro-n-butanoic acid (PFBA)/PFOA ratios were 2.8 and 0.72, respectively. These findings suggested shifting to the short-chain PFASs in the environment in China. To the authors knowledge this is the first study to document the levels of 6:2 Cl-PFESA, 8:2 Cl-PFESA in indoor dust., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Perfluoroalkyl substances (PFASs) are widely used synthetic chemicals, showing environmental/biological persistence and adverse effects on ecosystem and human health. Several epidemiological and animal studies have revealed that PFASs levels are associated with elevated serum insulin level; however, the effect of PFASs on insulin secretion and the underlying mechanism are not clear. In this study, the effect of a most concerned PFAS, perfluorooctane sulfonate (PFOS) on insulin secretion in Beta-TC-6 pancreatic cells was studied. The results showed that PFOS acute exposure stimulated insulin secretion and elevated intracellular calcium concentration ([Ca 2+ ] i ). The PFOS-stimulated [Ca 2+ ] i elevation was resulted from both extra- and intra-cellular sources. PFOS acute exposure decreased ATP content and ATP/ADP ratio, indicating the mitochondrial function was damaged under PFOS acute exposure. The PFOS-stimulated insulin secretion was inhibited by GW1100, a G Protein-coupled Receptor 40 (GPR40) specific inhibitor, but not affected by GW9662, a specific antagonist to the peroxisome proliferator-activated receptor gamma (PPARγ). The observation of RNA silencing further demonstrated that the PFOS-stimulated insulin secretion is, at least partially, via GPR40. By using specific inhibitors, we found that the GPR40 downstream pathways, phospholipase C (PLC) and L-type Ca 2+ channels (LTCC) were involved in PFOS-stimulated [Ca 2+ ] i elevation and insulin secretion., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Neutral polyfluoroalkyl and perfluoroalkyl substances (nPFASs) were detected in the surface water and sediment from the Haihe River (HR) and Dagu Drainage Canal (DDC), Tianjin, China. N-methyl perfluorooctane sulfonamide ethanol (MeFOSE) and N-ethyl perfluorooctane sulfonamide ethanol (EtFOSE) were the predominant nPFASs in surface water and sediment, which was different from the composition in air. The concentrations of ΣnPFASs in water from the HR (1.88-8.21 ng/L) were lower than those from the DDC (3.72-11.32 ng/L). Concentrations of ΣnPFASs were higher in the middle of the HR in the Dongli District due to industrial activity, whereas at lower reaches of the DDC, high ΣnPFAS concentrations might be due to effluent from wastewater treatment plants (WWTPs). The detection frequency in sediment (13.5%) was less than that in water (83%). The concentrations in sediment from the DDC (below limit of qualification (LOQ) to 5.58 ng/g) were higher than those from the HR (below LOQ to 2.46 ng/g). The distribution coefficient (log K D ) between water and sediment was calculated, and they were highly related to the compound structures. The contribution of nPFASs to nPFASs+PFAAs was up to 52% in sediment in the DDC, suggesting the importance of nPFASs in aquatic systems.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are anthropogenic chemicals widely used in industrial and consumer products. PFASs can be readily transported by water due to their relatively high solubility and polarity, and oceans are believed to be their final global sink. The heavily industrialized and urbanized Pearl River Delta in South China represents a major source of PFASs. In the present study, samples of surface waters, bottom waters, and sediments of the South China Sea (SCS) were collected during summer 2017 and 2018 to determine the level, distribution, and potential regional risk of PFASs. The PFAS concentrations in surface seawater, bottom seawater, and sediment were 125-1015 pg/L, 38-779 pg/L, and 7.5-84.2 pg/g dry weight, respectively. Perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA) were the dominant PFASs in seawater, while perfluorooctanesulfonic acid (PFOS) was dominant in sediment. The PFAS alternatives 6:2 and -8:2 Cl-polyfluorinated ether sulfonate (6:2 and 8:2 Cl-PFESA) as well as hexafluoropropylene oxide dimer (HFPO-DA) were detected in the SCS for the first time. The spatial distribution of PFASs in seawater and sediment were impacted by river outflows and sea currents, and concentrations decreased from the estuaries to the offshore regions due to the dilution effect. PFAS concentrations were relatively low compared to other coastal regions worldwide, and a preliminary environmental hazard assessment showed that PFASs posed minimal risk to marine organisms in the coastal region of the SCS, with the exception of PFOS., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A nationwide survey was conducted on per- and polyfluoroalkyl substances (PFASs) in precipitation across mainland China. Twenty-two PFASs, including precursors to perfluoroalkyl acids (pre-PFAAs), were investigated in thirty-nine precipitation samples collected from twenty-eight cities. Trifluoroacetate (TFA), perfluorooctanoic acid, and perfluorooctane sulfonic acid (PFOS) were ubiquitous in precipitation. TFA displayed the highest concentrations (8.8-1.8 × 10 3  ng/L), which were particularly elevated in coastal cities. 6:2 chlorinated polyfluorinated ether sulfonic acid, an alternative to PFOS, was detected for the first time in precipitation at a frequency of 43%. Polyfluoroalkyl phosphoric acid diesters and 6:2 fluorotelomer sulfonic acid were also occasionally detected. PFAS fluxes in the northeastern area (C4C12; 2.0 × 10 2 -3.4 × 10 3  ng/m 2 /d) with major PFAS manufacturing facilities were higher than those in the southwestern area (63-1.7 × 10 3  ng/m 2 /d). Using total oxidizable precursor (TOP) assay, the occurrence of unknown pre-PFAAs was for the first time uncovered in precipitation with maximum estimated fluxes of C6 and C8 pre-PFAAs at 3.1 × 10 3 and 4.3 × 10 3  ng/m 2 /d, respectively. The relative contribution of ultrashort-chain PFCAs (C2C3) ranged from 22% to 91% of ∑PFASs, while unknown pre-PFAAs accounted for 6%-56% of the total molar concentrations of PFASs. This bears critical concerns on underestimation of PFAS mass load from precipitation to surface environment ascribed to monitoring data solely on known PFASs. Unknown precursors of PFAAs in the atmosphere are yet to be identified for their chemical structures and relevant environmental risks as well., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Organic compounds could be taken up by plants via different pathways, depending on chemical properties and biological species, which is important for the risk assessment and risk control. To investigate the transport pathways of perfluoroalkyl acids (PFAAs) by wheat (Triticum acstivnm L.), the uptake of five perfluoroalkyl carboxylic acids (PFCAs): TFA (C2), PFPrA (C3), PFBA (C4), PFHxA (C6), PFOA (C8), and a perfluoroalkyl sulfonic acid: PFOS (C8)) were studied using hydroponic experiments. Various inhibitors including a metabolic inhibitor (Na 3 VO 4 ), two anion channel blockers (9-AC, DIDS), and two aquaporin inhibitors (AgNO 3 , glycerol) were examined. The wheat root and shoot showed different concentration trends with the carbon chain length of PFAAs. The uptake of TFA was inhibited by Na 3 VO 4 and 9-AC whereas PFPrA was inhibited by Na 3 VO 4 , AgNO 3 and 9-AC. For the other four PFAAs, only Na 3 VO 4 was effective. These results together with the result of concentration-dependent uptake, which followed the Michaelis-Menten model, indicate that the uptake of PFAAs by wheat is mainly an energy-dependent active process mediated by carriers. For the ultra-short chain PFCAs (C2 and C3), aquaporins and anion channels may also be involved. A competition between TFA and PFPrA was determined during the plant uptake but no competition was observed between these two shorter chain analogues with other analogues, neither between PFBA and PFHxA, PFBA and PFBS, PFOA and PFOS., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Forests serve as the primary reservoir for organic carbon above ground. Previous studies have revealed that forest soils play key roles in the retention of persistent organic pollutants (POPs). In this study, the occurrence and distribution of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) were investigated in 54 surface soil samples from 28 natural forested mountain sites across China between 2012 and 2013. The detection frequency of PFOA (70%) was significantly higher than that of PFOS (4%). PFOA levels ranged from <0.9 to 9.0 pg·g -1  dry weight (dw). Levels of PFOA and PFOS in forest soils were significantly lower than those in agricultural, urban and rural areas in China. Relatively high levels of PFOA were detected in Hubei Province (Jiugong Mountain, average: 3.4 pg·g -1  dw) and Jiangxi Province (Wugong Mountain, average: 4.4 pg·g -1  dw), where many domestic fluoropolymer manufacturers are located. PFOS was only detected in these two provinces (2.2 pg·g -1  dw and 2.7 pg·g -1  dw, respectively). From most of the surveyed mountains, the concentrations of PFOA increased with elevation. The lower temperature and greater precipitation probably made PFOA and its precursors available to transport and degrade more readily at higher altitude sites. A relatively higher level (1.9 ± 1.3 pg·g -1  dw) of PFOA was found in the broadleaf evergreen forest area, mainly due to the high industrial emissions, plant retention, and precipitation rate in this area. Source were the dominant factor controlling the spatial distribution of PFOA in natural forest soils in China., (Copyright © 2018. Published by Elsevier B.V.)

Modeling and predicting of a novel polar organic chemical integrative sampler (POCIS) for sampling of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) using molecularly imprinted polymers (MIPs) as receiving phase are presented in this study. Laboratory microcosm experiments were conducted to investigate the uptake kinetics, effects of flow velocity, pH, and dissolved organic matter (DOM), and also the selectivity of the POCIS. In this study, uptake study of PFOA and PFOS sampling on MIP-POCIS, over 14 days, was investigated. Laboratory calibrations of MIP-POCIS yielded sampling rate (R s ) values for PFOA and PFOS were 0.387 and 0.229 L/d, higher than POCIS using commercial sorbent WAX as receiving phase (0.133 and 0.141 L/d for PFOA and PFOS, respectively) in quiescent condition. The R s values for PFOA and PFOS sampling on MIP-POCIS were increased to 0.591 and 0.281 L/d in stirred condition (0.01 m/s), and no significant increase occurred when the flow velocity was further increased. The R s values were kept relatively high in the solution of which the pH was lower than the isoelectric point (IEP) of MIP-sorbent and decreased when the solution pH was extend the IEP value. Under the experimental conditions, DOM seemed to slightly facilitate the R s values of PFOA and PFOS in MIP-POCIS. The results showed that the interaction between the target compounds and the receiving phase was fully integrated by the imprinting effects and also the electrostatic interaction. Finally, comparing the sampling rate of WAX-POCIS and the MIP-POCIS, the MIP-POCIS offers promising perspectives for selective sampling ability for PFOA and PFOS.

Application of per- and polyfluoroalkyl substances (PFASs) is shifting to short-chain analogs (C ≤ 6) that raises concerns for their potential ecotoxicological risks. In the present study, pot experiments were carried out to study the effects of perfluoroalkyl acids (PFAAs), including perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs), with different carbon chain lengths (C4, C6, and C8) on the growth of wheat seedlings and their plant uptake and transfer at two spiking levels (200 and 2000 μg/kg soil). Exposure to C4 PFAAs slightly inhibited chlorophyll activity, whereas exposure to C8 PFAAs showed enhancement. The bioaccumulation factors (BAFs) for C4 PFAAs in wheat were over 10, while BAFs for C8 PFAAs were all below 1. Rhizospheric and root to shoot transfer factors for PFAAs were both negatively correlated with their log K ow (p < 0.05). PFCAs exhibited both higher rhizospheric mobility and accumulation potentials than PFSAs of the same chain lengths. Hence, perfluoroalkyl chain governs the mobility of PFAAs in a soil-plant system besides interactions of their head groups, and the substitution with shorter chain PFASs raises concerns for their higher plant accumulation potential that brings higher ecotoxicological and human exposure risks via food chains.

Industrial facilities can be point sources of per- and polyfluoroalkyl substances (PFASs) emission to the surrounding environment. In this study, 25 neutral and ionizable PFASs were analyzed in 94 multimedia samples including air, rain, outdoor settled dust, soil, plant leaves, river water, surface sediment, and shallow groundwater from two fluorochemical manufacturing parks (FMPs) in Fuxin, China, to elucidate the multimedia distribution and transfer pattern of PFASs from a point source. The concentrations of individual PFASs in air, outdoor settled dust, and surface river water decreased exponentially as the distance increases from the FMPs, whereas the concentrations of short-chain (C2-C4) perfluoroalkyl carboxylic acids (PFCAs) remained high (3000 ng/L) in the surface water 38 km away. At FMPs, air concentrations of fluorotelomer alcohols and iodides were found dominant with levels of up to 7900 pg/m 3 and 920 pg/m 3 , respectively. Trifluoroacetic acid was directly released from FMPs and occurred in all the environmental matrices at levels 1-2 orders of magnitude higher than other PFCAs. Higher air-water concentration ratios of short-chain PFCAs (C2-C4) suggested their transfer tendency from air to water. Both short-chain (C2) and long-chain (>C6) PFCAs have greater sediment-water distribution coefficients and deposit dust-air coefficients, which have great influences on the long-range transport potential of different analogues.

A newly developed solid-phase extraction cartridge composed of mixed sorbents was optimized for collection of both neutral and ionizable per- and polyfluoroalkyl substances (PFASs) in indoor air. Eighty-one indoor air samples and 29 indoor dust samples were collected from rooms of homes and hotels, textile shops, and cinemas in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the predominant PFASs found in air (250-82 300 pg/m 3 ) and hotel dust (24.8-678 ng/g). Polyfluoroalkyl phosphoric acid diesters were found at lower levels of nd-125 pg/m 3 in air and 0.32-183 ng/g in dust. Perfluoroalkyl carboxylic acids (PFCAs) were dominant ionizable PFASs in air samples (121-20 600 pg/m 3 ) with C4-C7 PFCAs contributing to 54% ± 17% of the profiles, suggesting an ongoing shift to short-chain PFASs. Long-chain PFCAs (C > 7) were strongly correlated and the intermediate metabolite of FTOHs, fluorotelomer unsaturated carboxylic acids, occurred in all the air samples at concentrations up to 413 pg/m 3 , suggesting the transformation of precursors such as FTOHs in indoor environment. Daily intake of ∑PFASs via air inhalation and dust ingestion was estimated at 1.04-14.1 ng/kg bw/d and 0.10-8.17 ng/kg bw/d, respectively, demonstrating that inhalation of air with fine suspended particles was a more important direct exposure pathway than dust ingestion for PFASs to adults.

Measurement of airborne perfluoroalkyl acids (PFAAs) is challenging, but important for understanding their atmospheric transport. Tree bark is good media for monitoring semivolatile compounds in the atmosphere. Whether it could work as an indicator of airborne PFAAs was first examined in this study. Bark and leaf samples collected around a Chinese fluorochemical manufacturing park (FMP) were analyzed for PFAAs and their branched isomers. Total PFAA concentrations (∑PFAAs) in the bark (mean, 279 ng/g dw) and leaf (250 ng/g dw) samples were comparable. ∑PFAAs in the barks collected within the boundaries of the FMP were significantly (p < 0.05) higher than those outside the FMP, and displayed a decreasing spatial trend as the distance from the FMP increased. However, such spatial difference and trend were not observed for the leaves. PFAA compositional profiles in most of the tree barks were consistent with each other, but different from those in tree leaves. These results indicated that tree barks mainly accumulated airborne PFAAs, while uptake from soil and translocation could make partial contribution to those in leaves. Perfluorooctanoate and perfluorooctanesulfonate in barks had strictly consistent isomeric compositions with their electrochemical fluorination products. Overall, these results indicated that the bark could be a good indicator of airborne PFAAs with respect to their occurrence, isomeric signature, and atmospheric transport.

A total of 23 per- and polyfluoroalkyl substances (PFASs) were investigated in the air, dry deposition, and plant leaves at two different landfills and one suburban reference site in Tianjin, China. The potential of landfills as sources of PFASs to the atmosphere and the phase distribution therein were evaluated. The maximum concentrations of ∑PFASs in the two landfills were up to 9.5 ng/m 3 in the air, 4.1 μg/g in dry deposition, and 48 μg/g lipid in leaves with trifluoroacetic acid and perfluoropropionic acid being dominant (71%-94%). Spatially, the distribution trend of ionizable and neutral PFASs in all three kinds of media consistently showed the central landfill > the downwind > the upwind > the reference sites, indicating that landfills are important sources to PFASs in the environment. Plant leaves were found effective in uptake of a variety of airborne PFASs including polyfluoroalkyl phosphoric acid diesters, thus capable of acting as a passive air sampling approach for air monitoring.

This work describes a novel method for the synthesis of molecularly imprinted polymers (MIPs) using 2-(trifluoromethyl) acrylic acid (TFMAA) and 4-vinyl pyridine (4-Vpy) as binary functional monomers, perfluorooctanoic acid (PFOA) as template, and ethyleneglycol dimethacrylate (EGDMA) as cross-linker in the presence of azobisisobutyronitrile (AIBN). The binary functional monomer MIPs were applied to selective recognition for PFOA and perfluorooctanesulfonic acid (PFOS) from aqueous environment. The MIPs were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and microscopic electrophoresis. Thereafter, the adsorption capacity and selectivity of the synthesized MIPs for PFOA and PFOS were evaluated by batch adsorption experiments. The maximum adsorption capacities of the MIPs for PFOA and PFOS were 6.42 and 6.27mg/g, respectively. It was also found that the adsorption capacities remained constant with increasing the solution pH in the range of 2.0-5.0, and then decreased when the pH was further increased. Finally, the novel MIPs can be reused after five cycles of adsorption-desorption-adsorption with no significant decrease of removal rate and have an effective performance in selective removal of PFOA and PFOS in real lake water samples. All the results indicate that the binary functional monomer MIPs have great potential to remove PFOA and PFOS in aqueous environment., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Per- and polyfluoroalkyl substances (PFASs) were detected in the atmosphere of a source region in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the dominant neutral PFASs in the atmosphere with total concentrations of 93.6-131 pg/m(3) and 8:2 FTOH contributing the most, whereas perfluorooctane sulfonamide derivatives (PFOSAs) were two magnitudes lower or undetected. In comparison, ionic PFASs (perfluoroalkyl carboxyl acids (PFCAs)) in the atmosphere were detected at similar or even higher levels. At wastewater treatment plants (WWTPs), the air over influent was found with higher levels of FTOHs than over aeration tank and effluent; whereas in the air over the aeration tank, the concentrations of PFOSAs and nonvolatile ionic PFASs substantially increased, suggesting a possible direct release of ionic PFASs to the atmosphere besides the atmospheric conversion from volatile precursors. In the air phase, a low proportion (1-5%) of PFCAs was subjected to dry deposition in the source region. Interestingly, the dry-deposition-to-bulk-air ratios of PFCA analogues were the lowest at medium chain lengths (C8 and C9) and increased with either shorter or longer chain length. The extraordinary affinity of shorter-chain PFCAs (C6-C7) to particles was presumed to be due to their smaller molecular size favoring the interactions between the carboxyl head groups and specific sorption sites on particulate matter., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

From eastern to western areas, per- and polyfluoroalkyl substances (PFASs) were detected at substantial levels in the outdoor dust across mainland China. Urban samples generally showed higher levels compared with those of rural samples. Compared with neutral PFASs, ionizable PFASs (C4-C12 perfluoroalkyl carboxylic acids and C4/C8 perfluoroalkyl sulfonic acids) were more abundant, with the highest total concentration up to 1.6 × 10(2) ng/g and perfluorooctanoic acid (PFOA) being a predominant analogue. Fluorotelomer alcohols (FTOHs) and polyfluoroalkyl phosphoric acid diesters (DiPAPs) were both detected in most samples with total concentrations of 0.12-32 and 0.030-20 ng/g, respectively. Perfluorooctane sulfonamidoethanols/sulfonamides (FOSE/As) were detected at low frequencies (<30%). In addition to partitioning to organic moiety, specific adsorption onto mineral particles can be important for PFASs to bind onto outdoor dust, especially for short-chain ionizable PFASs. The eastern plain areas were characterized by a higher contribution of long-chain ionizable PFASs; whereas the western high plateau areas were characterized by the dominating contribution of short-chain analogues. The difference suggests that the long-range atmospheric transport potential of PFASs from source regions to the inland is probably limited by the increase in altitude, and different sources from adjacent regions may influence the western border area of China.

Although levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in human blood are well documented, information on elimination of these chemicals is limited. In this study, PFOS and PFOA were analyzed in 81 whole blood-urine paired samples from general adults and pregnant women in Tianjin, China. PFOS and PFOA were detected in 48 and 76% of adult urine (AU) samples, with geometric mean (GM) concentrations of 0.011 and 0.008 ng/mL, respectively; whereas relatively low PFOS and PFOA concentrations were found in maternal urine (MU) samples, with GM concentrations of 0.006 and 0.003 ng/mL, respectively. For PFOA, the coefficients of Pearson's correlation between whole blood concentrations and creatinine-adjusted and creatinine-unadjusted urinary concentrations were 0.348 (p = 0.013) and 0.417 (p = 0.002), respectively. The GM urinary elimination rates of PFOS (PFOSUER) and PFOA (PFOAUER) were 16 and 25%, respectively, for adults. These results indicate that urine is an important pathway of excretion of perfluoroalkyl substances (PFASs). The partitioning ratios of PFAS concentration between urine and whole blood (PFASU/B) in pregnant women (PFOSU/B, 0.0004; PFOAU/B, 0.0011) were significantly lower (p = 0.025 for PFOSU/B, p = 0.017 for PFOAU/B) than the ratios found in non-pregnant women (PFOSU/B, 0.0013; PFOAU/B, 0.0028). Furthermore, our results suggest a clear gender difference in the urinary elimination of PFOA, with male adults (31%) having significantly higher PFOAUER than that of female adults (19%). PFOSUER was significantly inversely correlated with age (r = -0.334, p = 0.015); these findings suggest that urinary elimination of PFOS is faster in young adults than in the elderly.

Per- and poly-fluoroalkyl substances (PFASs) have been widely detected in the hydrosphere. The knowledge on the distribution and composition patterns of PFAS analogues with different chain length significantly contribute to their source analysis. In the present study, a regional scale investigation of PFASs in surface river waters and adjacent ground waters was carried out in two cities of China with potential contamination, Tianjin and Weifang. A total of 31 water samples were collected, and 20 PFASs therein were measured by a high-performance liquid chromatograph-tandem mass spectrometer (HPLC-MS/MS). The possible sources of PFASs in the aquatic environment were assessed primarily by concentration patterns as well as hierarchical cluster analysis. In all 4 rivers investigated in the two cities, perfluoroalkyl carboxylic acids (PFCAs) were the dominant compounds contributing over 70% of the PFASs detected. Perfluorooctanoic acid (PFOA) was the dominant PFCA with a concentration range of 8.58-20.3ng/L in Tianjin and 6.37-25.9ng/L in Weifang, respectively. On the average, the highest concentration was observed in samples from Dagu Drainage Canal (Dagu) in Tianjin and those short-chain PFASs (C4-C6) was detected with a comparable level of the longer-chain PFASs (>C6). Specifically, perfluorobutanoic acid (PFBA) was dominant in the short-chain analogues. This indicates that a remarkably increasing input of short-chain PFASs might be related to wastewater treatment plant effluent or industrial discharges, which could be possibly due to the switch of manufacturing to short-chain products. In Weifang, precipitation and subsequent surface runoff as non-point sources could be significant inputs of PFASs into surface water while groundwater was possibly subjected to severe point sources with ∑PFASs concentration up to ~100ng/L. The inconsistent distribution patterns in groundwater suggest complicated pathways of contamination., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Although levels of poly- and perfluoroalkyl substances (PFASs) in human maternal and neonatal blood have been widely reported in the literature, relationship of maternal-fetal transmission of PFASs with carbon chain length is presently not well understood. In this study, 11 PFASs were analyzed in matched samples, including not only maternal blood (MB, n = 31) and cord blood (CB, n = 30), but also placenta (n = 29) and amniotic fluid (AF, n = 29). Except for perfluorohexanoic acid (PFHxA), the detection frequencies of PFASs were similar among placenta, MB, and CB (>80% for 8 PFASs, nondetectable for 2 PFASs). Though only perfluorooctanoic acid (PFOA) was frequently detected (>90%) in AF, with a median concentration of 0.043 ng/mL, other 5 PFASs were also detectable in AF samples with low concentrations (mean: 0.013-0.191 ng/mL). This suggests that in addition to blood-borne in utero exposure, the fetus is also exposed to low levels of PFASs through AF. Concentrations of PFOA in AF were positively correlated with those in MB (r = 0.738, p < 0.01) and CB (r = 0.683, p < 0.001), suggesting that AF concentration could reflect fetal PFOA exposure during pregnancy and can be used as a biomarker. To clarify the effects of carbon chain length on maternal transfer of PFASs, we calculated maternal transfer efficiencies of PFASs from MB to CB (TMB-CB). A U-shaped trend in TMB-CB of C7-C12 perfluoroalkyl carboxylic acids (PFCAs) with increasing carbon chain length was found in this study for the first time. The U-shaped TMB-CB of PFCAs with carbon chain length is an integrated result of opposite trend of the ratios between MB/placenta and placenta/CB based on carbon chain length. This is the first study to report the occurrence of PFASs in human placenta. The results reported here enable better understanding of the maternal-fetal transmission of PFASs.

Twenty-three polychlorinated and perfluorinated compounds (PFCs) were investigated in water phase and particulate matters of 19 precipitation samples (18 snow samples and 1 rain sample) from different cities across eastern and central China collected in February 2010. The PFCs in samples of 9e precipitation events during more than half a year at 1 site in Tianjin and 6 successive samples during 1 precipitation event were measured to elucidate the change of PFC in precipitation. In addition, PFCs in 3 runoffs at different kinds of sites in Tianjin were compared with those in the corresponding precipitation. The results showed that the particulate matters separated from the precipitation contained undetectable PFCs. The total PFC concentration ranged between 4.7 and 152 ng L(-1) in water phase of the precipitation samples, with perfluorooctanoic acid (PFOA) being detected at all of the sampling sites and the dominant PFC at most of the sampling sites. Some potential precursors of environmentally concerned PFCs and their degradation intermediates were measured simultaneously, among which 6:2 fluorotelomer unsaturated carboxylic acid (6:2 FTUCA), 8:2 FTUCA, and  × (3, 4, 5, 7):3 acid [F(CF(2))xCH(2)CH(2)COOH] were measured for the first time in Chinese precipitations; however, their concentrations were all lower than the limits of detection except that 6:2 FTUCA and 8:2 FTUCA could be detected in 3 and 8 precipitation samples, respectively. No clear seasonal variation in PFC concentrations in precipitation was observed during half a year; however, a relatively greater average concentration of total PFCs was observed during winter and summer compared with spring. The concentration of individual PFCs showed an obvious descending trend in the successive samples of the precipitation event. PFOA and perfluorononanoic acid in runoffs collected from different sites showed the following similar pattern-gas station > highway > university campus-whereas the other detected PFCs had no concurrent trend.

The 6:2 FTOH [F(CF(2))(6)CH(2)CH(2)OH] is a major raw material being used to replace 8:2 FTOH [F(CF(2))(8)CH(2)CH(2)OH] to make FTOH-based products for industrial and consumer applications. A novel aerobic sediment experimental system containing 20 g wet sediment and 30 mL aqueous solution was developed to study 6:2 FTOH biotransformation in river sediment. 6:2 FTOH was dosed into the sediment to follow its biotransformation and to analyze transformation products over 100 d. The primary 6:2 FTOH biotransformation in the aerobic sediment system was rapid (T(1/2)<2d). 5:3 acid [F(CF(2))(5)CH(2)CH(2)COOH] was observed as the predominant polyfluorinated acid on day 100 (22.4 mol%), higher than the sum of perfluoropentanoic acid (10.4 mol%), perfluorohexanoic acid (8.4 mol%), and perfluorobutanoic acid (1.5 mol%). Perfluoroheptanoic acid was not observed during 6:2 FTOH biotransformation. The 5:3 acid can be further degraded to 4:3 acid [F(CF(2))(4)CH(2)CH(2)COOH, 2.7 mol%]. This suggests that microbes in the river sediment selectively degraded 6:2 FTOH more toward 5:3 and 4:3 acids compared with soil. Most of the observed 5:3 acid formed bound residues with sediment organic components and can only be quantitatively recovered by post-treatment with NaOH and ENVI-Carb™ carbon. The 6:2 FTCA [F(CF(2))(6)CH(2)COOH], 6:2 FTUCA [F(CF(2))(5)CF=CHCOOH], 5:2 ketone [F(CF(2))(5)C(O)CH(3)], and 5:2 sFTOH [F(CF(2))(5)CH(OH)CH(3)] were major transient intermediates during 6:2 FTOH biotransformation in the sediment system. These results suggest that if 6:2 FTOH or 6:2 FTOH-based materials were released to the river or marine sediment, poly- and per-fluorinated carboxylates could be produced., (Copyright © 2012 Elsevier Ltd. All rights reserved.)