P-perfluorous Nonenoxybenzene Sulfonate Research Articles

Legacy and emerging per- and polyfluoroalkyl substances in tissue and toilet paper from China

Per- and polyfluoroalkyl substances (PFASs) have been found in toilet paper in Europe, the United States, and Africa; however, their presence in Chinese household paper has not been investigated. In this study, 21 legacy and 30 emerging PFASs were analyzed in tissue and toilet paper from China, including 48 samples of different origins and materials. Median concentrations of chlorinated polyfluorinated ether sulfonates (Cl-PFESAs), hexafluoropropylene oxide homologs (HFPOs), and p-perfluorous nonenoxybenzenesulfonate (OBS) were 0.32, 0.19, and 0.10 ng/g dry weight (dw), respectively. The detection frequencies (DFs) of Cl-PFESAs and OBS both were greater than 96%, followed by hexafluoropropylene oxide trimer acid (HFPO-TrA, DF: 85%). Notably, the level of HFPO-TrA in one sample was as high as 540 ng/g dw, indicating a potential environmental risk to humans. In addition, the concentrations of Cl-PFESAs in toilet paper were significantly higher than that in tissue (p < 0.05). However, no significant differences were observed in the concentrations of PFASs in tissue and toilet paper from different materials and origins. This suggests that PFASs, particularly emerging PFASs, are widely detected in tissue and toilet paper products across China, and their presence is a potential source of landfill contamination and human exposure.

Emerging and legacy per- and polyfluoroalkyl substances in Daling River and its estuary, Northern China

Strict restriction on legacy per- and polyfluoroalkyl substances (PFASs) has caused a dramatic increase in production and usage of emerging PFASs over the last decades. However, the environmental behaviors of emerging PFASs is largely unknown in Daling River, Northern China. In this study, the potential sources, sediment-water partitioning and substitution trends of PFASs were investigated in overlying water and sediments from Daling River and its estuary. Perfluorooctane sulfonate and 6:2 fluorotelomer sulfonic acid were major compounds, and sodium p-perfluorous nonenoxybenzene sulfonate was first detected. Firefighting foam manufacturing and fluoropolymer production were the main sources of PFASs. Compared to legacy PFASs (C8), the emerging PFASs (C6 - C9) were more incline to distribute into overlying water. Substitution trends indicated 6:2 fluorotelomer sulfonic acid and hexafluoropropylene oxide trimer acid as the important alternatives of perfluorooctane sulfonate and perfluorooctanoic acid, respectively. The results were meaningful for understanding the environmental behaviors of emerging PFASs.

Sodium p-perfluorous nonenoxybenzene sulfonate induces ROS-mediated necroptosis by directly targeting catalase in HepG2 cells

Sodium p-perfluorous nonenoxybenzene sulfonate (OBS) has been widely used as a substitute for perfluorooctane sulfonic acid (PFOS) because of its high surface activity and low cost, but the knowledge of its biological effects is still limited. In this study, we compared the toxic effects of OBS and PFOS on human hepatoma cells (HepG2). OBS resulted in lower cell viability, higher ROS levels, and more severe necrosis than PFOS, indicating that OBS caused higher cytotoxicity than PFOS. In this process, OBS induced a burst of ROS and downregulation of catalase (CAT). OBS-induced oxidative stress was recovered after the CAT overexpression, but the CAT levels were not reversed after N-acetylcysteine (NAC) pretreatment. This indicates that the downregulated CAT is an upstream signal of the ROS burst. Moreover, drug affinity targeting assay, spectroscopic analysis and molecular docking were conducted, showing that OBS directly targeted CAT and therefore downregulated CAT. In addition, we found that OBS-induced necrosis is RIP1/RIP3-dependent programmed necroptosis. In summary, OBS directly targets CAT to reduce CAT levels and induces oxidative stress and necroptosis. Our findings are helpful to understand the toxicity of OBS and to evaluate the safety of OBS as a substitute for PFOS.

Further Insight into Extractable (Organo)fluorine Mass Balance Analysis of Tap Water from Shanghai, China.

The ubiquitous occurrence of per- and polyfluoroalkyl substances (PFAS) and the detection of unexplained extractable organofluorine (EOF) in drinking water have raised growing concerns. A recent study reported the detection of inorganic fluorinated anions in German river systems, and therefore, in some samples, EOF may include some inorganic fluorinated anions. Thus, it might be more appropriate to use the term "extractable fluorine (EF) analysis" instead of the term EOF analysis. In this study, tap water samples (n = 39) from Shanghai were collected to assess the levels of EF/EOF, 35 target PFAS, two inorganic fluorinated anions (tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-)), and novel PFAS through suspect screening and potential oxidizable precursors through oxidative conversion. The results showed that ultra-short PFAS were the largest contributors to target PFAS, accounting for up to 97% of ΣPFAS. To the best of our knowledge, this was the first time that bis(trifluoromethanesulfonyl)imide (NTf2) was reported in drinking water from China, and p-perfluorous nonenoxybenzenesulfonate (OBS) was also identified through suspect screening. Small amounts of precursors that can be oxidatively converted to PFCAs were noted after oxidative conversion. EF mass balance analysis revealed that target PFAS could only explain less than 36% of EF. However, the amounts of unexplained extractable fluorine were greatly reduced when BF4- and PF6- were included. These compounds further explained more than 44% of the EF, indicating the role of inorganic fluorinated anions in the mass balance analysis.

Novel PFOS alternative OBS inhibits body growth of developing zebrafish by triggering thyroid function disorder and osteoclast differentiation

The extensive use of the perfluorooctane sulfonate (PFOS) alternative sodium p-perfluorous nonenoxybenzene sulfonate (OBS) has resulted in its widespread detection in the environment and enrichment in wildlife and humans. However, little is known about its potential toxicity, particularly in terms of body development. In this study, zebrafish embryos were acutely exposed to PFOS and OBS for a comparative developmental toxicity assessment. Both PFOS and OBS led to lower body weight and shorter body length, and the damaging effects of PFOS were more severe than those of OBS at the same exposure concentration. Biochemical assays of THs and transcription profiles correlated to the HPT axis demonstrated that OBS-induced body development inhibition resulted mainly from interference in THs synthesis, transfer, coupling with receptors, and conversion from T4 to T3, which was similar to the case of PFOS, except that the disruptive effects of OBS on thyroid function were more intense. Further transcriptome analysis showed that PFOS and OBS also promoted osteoclast differentiation, aggravating the inhibitory effects on body growth, and that PFOS had more obvious inhibitory effects than OBS. This study systematically explored the inhibitory effects of PFOS and OBS exposure on body development and tightly linked the toxic effects to thyroid function disorder and osteoclast differentiation. Our findings highlight that the health risks associated with OBS, an emerging substitute for PFOS, should not be ignored.

Comparative stress response assessment of PFOS and its alternatives, F-53B and OBS, in wheat: An insight of toxic mechanisms and relative magnitudes

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.

The novel polyfluoroalkyl benzenesulfonate OBS exposure induces cell cycle arrest and senescence of rat pituitary cell GH3 via the p53/p21/RB pathway

Sodium p-perfluorous nonenoxybenzene sulfonate (OBS), an economical alternative to perfluorooctane sulfonate (PFOS) in multiple industrial fields, is widely detected in the environment. The toxicity of OBS has received increasing attention. Pituitary cells are components of the endocrine system and act as vital regulators of homeostatic endocrine balance. However, the effects of OBS on pituitary cells remain unknown. The present study explores the effects of OBS (0.5, 5, and 50 μM) on GH3 rat pituitary cells after treatment for 24, 48, and 72 h. We found that OBS significantly inhibited cell proliferation in GH3 cells with remarkable senescent phenotypes, including enhanced SA-β-gal activity and expression of senescence-associated secretory phenotype (SASP)-related genes, cell cycle arrest, and upregulation of the senescence-related proteins γ-H2A.X and Bcl-2. OBS caused significant cell cycle arrest of GH3 cells at the G1-phase and concomitantly downregulated the expression of some key proteins for the G1/S transition, including cyclin D1 and cyclin E1. Consistently, the phosphorylation of retinoblastoma (RB), which plays a central role in regulating the cell cycle, was prominently reduced after OBS exposure. Furthermore, OBS notably activated the p53-p21 signalling pathway in GH3 cells, as evidenced by increased p53 and p21 expressions, enhanced p53 phosphorylation, and augmented p53 nuclear import. To our knowledge, this study is the first to reveal that OBS triggers senescence in pituitary cells via the p53-p21-RB signalling pathway. Our study demonstrates a novel toxic effect of OBS in vitro, and provides new perspectives for understanding the potential toxicity of OBS.

A review of cardiovascular effects and underlying mechanisms of legacy and emerging per- and polyfluoroalkyl substances (PFAS).

Cardiovascular disease (CVD) poses the leading threats to human health and life, and their occurrence and severity are associated with exposure to environmental pollutants. Per- and polyfluoroalkyl substances (PFAS), a group of widely used industrial chemicals, are characterized by persistence, long-distance migration, bioaccumulation, and toxicity. Some PFAS, particularly perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonic acid (PFHxS), have been banned, leaving only legacy exposure to the environment and human body, while a number of novel PFAS alternatives have emerged and raised concerns, such as polyfluoroalkyl ether sulfonic and carboxylic acid (PFESA and PFECA) and sodium p-perfluorous nonenoxybenzene sulfonate (OBS). Overall, this review systematically elucidated the adverse cardiovascular (CV) effects of legacy and emerging PFAS, emphasized the dose/concentration-dependent, time-dependent, carbon chain length-dependent, sex-specific, and coexposure effects, and discussed the underlying mechanisms and possible prevention and treatment. Extensive epidemiological and laboratory evidence suggests that accumulated serum levels of legacy PFAS possibly contribute to an increased risk of CVD and its subclinical course, such as cardiac toxicity, vascular disorder, hypertension, and dyslipidemia. The underlying biological mechanisms may include oxidative stress, signaling pathway disturbance, lipid metabolism disturbance, and so on. Various emerging alternatives to PFAS also play increasingly prominent toxic roles in CV outcomes that are milder, similar to, or more severe than legacy PFAS. Future research is recommended to conduct more in-depth CV toxicity assessments of legacy and emerging PFAS and explore more effective surveillance, prevention, and treatment strategies, accordingly.

Effects of PFOS, F-53B and OBS on locomotor behaviour, the dopaminergic system and mitochondrial function in developing zebrafish (Danio rerio)

Perfluorooctanesulfonic acid (PFOS) has widely been reported to persist in the environment and to elicit neurotoxicological effects in wildlife and humans. Following the restriction of PFOS use, 6:2 chlorinated polyfluorinated ether sulfonate (F-53B) and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) have emerged as novel PFOS alternatives and have been detected in the environment. However, knowledge on the toxicological effects of these alternatives remains scarce. Using developing transgenic Tg(dat:eGFP) zebrafish, we evaluated the consequences of exposure to 0, 0.1 and 1 mg/l PFOS, F-53B and OBS on the dopaminergic system, locomotor behaviour and mitochondrial function. All compounds generally reduced locomotor activity under light conditions irrespective of exposure concentration. Exposure to OBS (at all concentrations), as well as PFOS and F-53B (at 1 mg/l), significantly reduced subpallial dopaminergic neuron abundance. PFOS also significantly reduced dat and pink1 expression irrespective of exposure concentration, while F-53B and OBS tended to reduce mitochondrial pink1 and fis1 expression across concentrations without reaching statistical significance. Mitochondrial function, in the form of reduced oxygen consumption rate and marginally inhibited ATP-linked oxygen consumption rate, was affected only in response to 1 mg/l PFOS. Together, PFOS and the emerging contaminants F-53B and OBS inhibit locomotion at similar concentrations, a finding correlated with decreased dopaminergic neuron numbers in the subpallium and decreased expression of pink1. These findings are relevant to wildlife and human health, as they suggest that PFOS as well as replacement compounds affect locomotion likely in part by negatively impacting the dopamine system.

Emerging poly- and perfluoroalkyl substances in water and sediment from Qiantang River-Hangzhou Bay

Many emerging poly- and perfluoroalkyl substances (PFASs) are being used in China, due to the gradual phase out of legacy PFASs. Occurrence and environmental behaviors of emerging PFASs in Chinese fresh water environment are still not well known. In this study, 31 PFASs, including 14 emerging PFASs, were measured in 29 pairs of water and sediment samples from Qiantang River-Hangzhou Bay, an important drinking water resource for cities in Yangtze River basin. Perfluorooctanoate was consistently the predominant legacy PFAS in water (8.8–130 ng/L) and sediment (3.7–49 ng/g dw). Twelve emerging PFASs were detected in water, with the dominance of 6:2 chlorinated polyfluoroalkyl ether sulfonates (6:2 Cl-PFAES; mean 11 ng/L, 0.79–57 ng/L) and 6:2 fluorotelomer sulfonate (6:2 FTS; 5.6 ng/L, < LOD–29 ng/L). Eleven emerging PFASs were found in sediment, and were also dominated by 6:2 Cl-PFAES (mean 4.3 ng/g dw, 0.19–16 ng/g dw) and 6:2 FTS (2.6 ng/g dw, < LOD–9.4 ng/g dw). Spatially, sampling sites closed to the surrounding cities had comparatively higher water concentrations of PFASs. Among emerging PFASs, 8:2 Cl-PFAES (3.0 ± 0.34) had the highest mean field-based log-transformed organic‑carbon normalized sediment-water partition coefficient (log Koc), followed by 6:2 Cl-PFAES (2.9 ± 0.35) and hexafluoropropylene oxide trimer acid (2.8 ± 0.32). p-perfluorous nonenoxybenzene sulfonate (2.3 ± 0.60) and 6:2 FTS (1.9 ± 0.54) had relatively lower mean log Koc values. To our knowledge, this is the most comprehensive study investigating the occurrence and partitioning behaviors of emerging PFASs in Qiantang River.

Insights into the circadian rhythm alterations of the novel PFOS substitutes F-53B and OBS on adult zebrafish

As alternatives to perfluorooctane sulfonate (PFOS), 6:2 Cl-PFESA (F-53B) and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) are frequently detected in aquatic environments, but little is known about their neurotoxicity, especially in terms of circadian rhythms. In this study, adult zebrafish were chronically exposed to 1 μM PFOS, F-53B and OBS for 21 days taking circadian rhythm-dopamine (DA) regulatory network as an entry point to comparatively investigate their neurotoxicity and underlying mechanisms. The results showed that PFOS may affect the response to heat rather than circadian rhythms by reducing DA secretion due to disruption of calcium signaling pathway transduction caused by midbrain swelling. In contrast, F-53B and OBS altered the circadian rhythms of adult zebrafish, but their mechanisms of action were different. Specifically, F-53B might alter circadian rhythms by interfering with amino acid neurotransmitter metabolism and disrupting blood-brain barrier (BBB) formation, whereas OBS mainly inhibited canonical Wnt signaling transduction by reducing cilia formation in ependymal cells and induced midbrain ventriculomegaly, finally triggering imbalance in DA secretion and circadian rhythm changes. Our study highlights the need to focus on the environmental exposure risks of PFOS alternatives and the sequential and interactive mechanisms of their multiple toxicities.

Bioaccumulation and biomagnification of emerging poly- and perfluoroalkyl substances in marine organisms

Accumulating evidence has demonstrated the wide environmental presence of 6:2 chlorinated polyfluoroalkyl ether sulfonates (6:2 Cl-PFAES) and p-perfluorous nonenoxybenzene sulfonate (PFNOBS). However, data on the bioaccumulation and trophic magnification of these emerging poly- and perfluoroalkyl substances (PFASs) in subtropical marine environment is still limited. In this study, seawater (n = 17), sediment (n = 14), and marine organism (27 species; n = 177) samples were collected from East China Sea, and analyzed them for legacy and emerging PFASs. Besides perfluoroalkyl carboxylates and perfluorooctane sulfonate (PFOS), 6:2 Cl-PFAES was always among the predominant PFASs detected in seawater, sediment, and marine organism. For emerging PFASs, 6:2 Cl-PFAES (mean ± SD, 3.1 ± 0.17), 8:2 Cl-PFAES (3.3 ± 0.35), and PFNOBS (3.3 ± 0.19) had lower bioaccumulation factors (BAF) than PFOS (3.4 ± 0.22) in marine fish. In crab, PFNOBS (3.7 ± 0.33) had a lower biota-sediment accumulation factor (BSAF) than PFOS (3.9 ± 0.45). In snail, among all detected PFASs, PFNOBS (4.0 ± 0.42) had the highest mean log BSAF value. 8:2 Cl-PFAES consistently had a higher log BSAF value than 6:2 Cl-PFAES in snail and crab. Notably, these differences in BAF and BSAF are not significant. Among PFASs, 6:2 Cl-PFAES (2.3; 95 % confidence interval, CI: 1.9–2.6) displayed the highest trophic magnification factor (TMF). PFNOBS had the lowest TMF value (1.8, 95 % CI: 1.4–2.1), but which still indicates its weak biomagnification through the current marine food web. This is the first study reporting the bioaccumulation and biomagnification of PFNOBS in marine organisms, which deepens the understanding of its environmental behavior in the marine ecosystem.

Aberrant hepatic lipid metabolism associated with gut microbiota dysbiosis triggers hepatotoxicity of novel PFOS alternatives in adult zebrafish.

Perfluorooctane sulfonate (PFOS) has been reported to induce hepatotoxicity in wildlife and humans. Novel PFOS alternatives have been widely used following restrictions on PFOS, but little is known about their potential toxicity. Here, the first comprehensive investigation on the chronic hepatotoxicity and underlying molecular mechanisms of PFOS, 6:2Cl-PFESA (F-53B), and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) was carried out on adult zebrafish through a histopathological examination, biochemical measurement, and multi-omics analysis. PFOS and its alternatives caused changes in liver histopathology and liver function indices in the order of F-53B>PFOS>OBS, which was consistent with their concentration in the liver. In silico modeling and transcriptional profiles suggested that the aberrant hepatic lipid metabolism induced by F-53B and PFOS was initiated by the action on peroxisome proliferator-activated receptor γ (PPARγ), which triggered changes in downstream genes transcription and led to an imbalance between lipid synthesis and expenditure. Gut microbiome analysis provided another novel mechanistic perspective that changes in the abundance of Legionella, Ralstonia, Brevundimonas, Alphaproteobacteria, Plesiomonas, and Hyphomicrobium might link to alterations in the PPAR pathway based on their significant correlation. This study provides insight into the molecular mechanisms of hepatotoxicity induced by PFOS and its novel alternatives and highlights the need for concern about their environmental exposure risks.

Tissue distribution of sodium p-perfluorous nonenoxybenzene sulfonate (OBS) in mice via oral exposure.

Environmental risks caused by emerging per- and polyfluoroalkyl substances (PFASs) have attracted increasing attention. As an important substitute for perfluorooctane sulfonate (PFOS), sodium p-perfluorous nonenoxybenzene sulfonate (OBS) is widely used as a firefighting foam additive and oil recovery agent in China. This study reported the tissue distribution of OBS in KM mice that were administered a dose of OBS at 10µg/day via daily oral gavage for 7, 14, or 28days. During exposure, gender-based differences were observed in body weight changes and tissue distribution of OBS. Liver exhibited the highest concentrations (males: 12.57±1.80µg/g; females: 11.80±5.32µg/g) and tissue/blood ratios and contributed more than 50% to the whole-body burden of OBS in both male and female mice, showing its ability to enrich PFASs. Furthermore, there were certain differences in the distribution characteristics of the three OBS isomers. Based on its bioaccumulation potential and widespread use, further studies are required on the human exposure risks of OBS.

Maternal Sodium p-Perfluorous Nonenoxybenzene Sulfonate Exposure Disturbed Lipid Metabolism and Induced an Imbalance in Tyrosine Metabolism in the F1 Generation of Mice.

The toxicity of perfluorinated compounds (PFCs) to mammals has recently received increasing attention. However, the effects of maternal sodium p-perfluorous nonenoxybenzene sulfonate (OBS) exposure during pregnancy and lactation on the liver function of dams (F0) and offspring (F1) mice are still unknown. The results demonstrated that maternal OBS treatment could not only induce lipid metabolism dysfunction but also disrupt amino acid metabolism in the liver of F0 and F1 generations. OBS had marked accumulation in the liver, and the serum and liver triglyceride (TG) levels increased in the F0 and F1 generations after maternal OBS exposure. Moreover, maternal OBS exposure changed the transcriptional levels of genes related to lipid metabolism (fatty acid (FA) synthesis, TG synthesis, and transport) and induced changes in the amino acid level in dams and 20-day-old mice offspring (F1-20 d). Additionally, the regulation of lipid metabolism by OBS was mainly dependent on the activation of peroxisome proliferator-activated receptor γ (PPARγ) and cluster of differentiation 36 (CD36). Interestingly, OBS could also disturb tyrosine (TYR) metabolism by increasing the TYR level and downregulating fumarate acetoacetate hydrolase (FAH). Together, these results indicated that the liver can be perceived as the major target tissue of OBS, which strongly affected metabolic function and ultimately led to an imbalance in the metabolism of lipids and TYR. In summary, maternal OBS exposure during pregnancy and lactation has toxic effects on the hepatic metabolism of dams and offspring, indicating that the toxic effects could obviously cross generations of mice, and we should pay more attention to understanding the health risk to both dams and offspring.

Oligolayered Co@MXene with a Co···SO3 cation-π bridge for ultra-rapid catalytic oxidation of a novel “forever chemical” OBS

Sodium p-perfluorous nonenoxybenzene sulfonate (OBS) as a novel alternative to perfluorooctane sulfonate (PFOS), belongs to the family of per- and polyfluoroalkyl substances (PFASs). We demonstrated that Co-based oligolayered MXene (Co@o-MXene) achieved the complete oxidation of OBS during catalytic ozonation with peroxymonosulfate (PMS). The optimized catalyst exhibited 78.5% OBS oxidation in only 2 min, and the oxidation route was thoroughly investigated by Fukui function calculations and QTOF-MS/MS analysis. However, within the fluoroprotein (FP) foam solution, high TOC removal was performed via the newly designed two-stage ozonation process. Systematic studies indicated that OBS can donate electrons through a Co···SO3 cation-π bridge on the surface of o-MXene/PMS accompanied by the generation of reactive oxygen species (ROS), the strong adsorption energy (Eads) value of PMS, enhanced total density of states (TDOS) and uneven electron density in this reaction system. This work extended the potential of newly developed MXene family materials to decompose PFAS.

Spatiotemporal distribution, partitioning behavior and flux of per- and polyfluoroalkyl substances in surface water and sediment from Poyang Lake, China

Thirty-five legacy and emerging per- and polyfluoroalkyl substances (PFAS) were analyzed in surface water and sediments collected from Poyang Lake, the largest freshwater lake in China. The ƩPFAS concentrations ranged from 23 to 1000 ng/L in water dissolved phase, 1.3–9.8 ng/L in suspended particulate matters, and 0.26–2.9 ng/g dry weight in sediments. Short-chain and emerging PFAS were predominant in surface water and sediments, rather than legacy perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Hexafluoropropylene oxide dimer/trimer acid (HFPO-DA/TA), 6:2 and 8:2 chlorinated polyfluorinated ether sulfonic acids (6:2 and 8:2 Cl-PFESAs), 6:2 fluorotelomer sulfonate (6:2 FTS), and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) were detected in all samples, indicating that these emerging PFAS have been widely produced and used in this region. The high concentrations of HFPO-DA/TA, 6:2 FTS, 6:2, 8:2 Cl-PFESAs, and OBS in sediments and their higher water–sediment distribution coefficients than those of predecessors (PFOA or PFOS) suggest that lake sediments could be an important long-term sink for these emerging alternatives. The positive matrix factorization model demonstrated that food packaging and textile treatments (50%) and fluoropolymer manufacturing (26% for alternative sources and 8.2% for legacy sources) were the two major sources of PFAS in Poyang Lake. The influx and outflux of total PFAS in Poyang Lake were 9.0 and 12.8 ton/year, respectively, and the OBS flux was estimated for the first time. The results provide insights into the environmental behavior and fate of emerging PFAS in freshwater ecosystems.

Comparative chronic toxicities of PFOS and its novel alternatives on the immune system associated with intestinal microbiota dysbiosis in adult zebrafish

6:2 Chlorinated polyfluorinated ether sulfonate (F-53B) and sodium p-perfluorous nonenoxybenzene sulfonate (OBS) are widely used as perfluorooctane sulfonate (PFOS) alternatives in the Chinese market. Here, adult zebrafish were chronically exposed to 1 μM PFOS, F-53B, and OBS for 21 days to investigate the comparative immunotoxicity of these three per- and polyfluoroalkyl substances (PFAS). PFOS induced more severe oxidative stress in the liver than F-53B and OBS, and these three PFAS induced similar anti-inflammatory effects by repressing the expression of pro-inflammatory cytokines. The intestinal microbiota analysis showed that the relative abundance of Plesiomonas, Aeromonas, Cetobacterium, Shewanella, and Vibrio changed with the same trend in the three PFAS treatment groups. Furthermore, the PFAS increased the expression of hepcidin, muc, the immune-related genes mpo and saa, and decreased the expression of the tight junction-related gene occ in the intestine; moreover, villus height of the intestine was reduced after PFAS exposure, which indicated the functional disruption of the intestine. In particular, the significant correlation between the changed intestinal microbiota and liver and intestinal indicators also suggested the interaction between the immune system and intestinal microbiota. Taken together, our results indicate that exposure to PFOS and its alternatives F-53B and OBS can induce hepatic immunotoxicity associated with intestinal microbiota dysbiosis in adult zebrafish.

Legacy and emerging poly- and perfluorochemicals in seawater and sediment from East China Sea

Following the global phase out of perfluorooctane sulfate (PFOS), chlorinated polyfluoroalkyl ether sulfonates (Cl-PFAESs) and p-perfluorous nonenoxybenzenesulfonate (PFNOBS) have emerged as novel PFOS substitutes. However, until now, limited data is available on their occurrence and environmental behaviors in the marine environment. Here, seawater and sediment samples were collected from East China Sea and analyzed for Cl-PFAESs, PFNOBS, and perfluoroalkyl acids (PFAAs; including their branched isomers) to investigate their concentrations, potential sources, and sediment-seawater partitioning behaviors. Perfluorooctanoate (PFOA) and PFOS were consistently the predominant PFAAs in seawaters and sediments. Branched PFOA and PFOS isomers were consistently much less frequently detected in sediments than that in seawaters. Linear PFOA contributed 92–95% of total PFOA in seawaters, suggesting the great contribution of telomerization PFOA. 6:2 Cl-PFAES was detected in all seawaters (concentration, 0.58–47 pg/L) and in the majority of sediments (<LOD–28 pg/g). PFNOBS was observed in 46% of seawater samples (concentration, <LOD–5.2 pg/L) and 66% of sediment samples (<LOD–1.7 pg/g). Spatial distribution trend suggested the riverine input as an important source of PFAAs and 6:2 Cl-PFAES in this sampling area. 6:2 Cl-PFAES (log Koc, 2.6 ± 0.36) and PFNOBS (2.7 ± 0.33) had comparable mean log-transformed sediment-seawater partitioning coefficients (log Koc) to PFOA (2.5 ± 0.32) or PFOS (2.8 ± 0.49), indicating their long-range transport potential in global oceans with ocean currents. Overall, this study provides the first data on occurrence and partitioning behaviors of 6:2 Cl-PFAES and PFNOBS in the marine environment.

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate (OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate (OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions, further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.