Per- and polyfluoroalkyl substances in Chinese commercially available red swamp crayfish (Procambarus clarkii): Implications for human exposure and health risk assessment.

The extensive utilization of per- and polyfluoroalkyl substances (PFASs) has led to their pervasive presence in the environment, resulting in contamination of aquatic products. Prolonged exposure to PFASs has been linked to direct hepatic and renal damage, along with the induction of oxidative stress, contributing to a spectrum of chronic ailments. Despite the recent surge in popularity of red swamp crayfish as a culinary delicacy in China, studies addressing PFASs' exposure and associated health risks from their consumption remain scarce. To address this gap, our study investigated the PFASs' content in 85 paired edible tissue samples sourced from the five primary red swamp crayfish breeding provinces in China. The health risks associated with dietary exposure were also assessed. Our findings revealed widespread detection of PFASs in crayfish samples, with short-chain perfluoroalkyl carboxylic acids (PFCAs) exhibiting the highest concentrations. Notably, the total PFAS concentration in the hepatopancreas (median: 160 ng/g) significantly exceeded that in muscle tissue (5.95 ng/g), as did the concentration of every single substance. The hazard quotient of perfluorohexanesulfonic acid (PFHxS) via consuming crayfish during peak season exceeded 1. In this case, a potential total non-cancer health risk of PFASs, which is mainly from the hepatopancreas and associated with PFHxS, is also observed (hazard index>1). Thus, it is recommended to avoid consuming the hepatopancreas of red swamp crayfish. Greater attention should be paid to governance technology innovation and regulatory measure strengthening for short-chain PFASs.

Population exposure to emerging perfluoroalkyl acids (PFAAs) via drinking water resources: Application of multivariate statistics and risk assessment models.

This study assessed the occurrence, origins, and potential risks of emerging perfluoroalkyl acids (PFAAs) for the first time in drinking water resources of Khyber Pakhtunkhwa, Pakistan. In total, 13 perfluoroalkyl carboxylic acids (PFCAs) with carbon (C) chains C4-C18 and 4 perfluoroalkyl sulfonates (PFSAs) with C chains C4-C10 were tested in both surface and ground drinking water samples using a high-performance liquid chromatography system (HPLC) equipped with an Agilent 6460 Triple Quadrupole liquid chromatography-mass spectrometry (LC-MS) system. The concentrations of ∑PFCAs, ∑PFSAs, and ∑PFAAs in drinking water ranged from 1.46 to 72.85, 0.30-8.03, and 1.76-80.88 ng/L, respectively. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) were the dominant analytes in surface water followed by ground water, while the concentration of perfluorobutane sulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), and perfluorododecanoic acid (PFDoDA) were greater than long-chain PFOA and PFOS. The correlation statistics, which showed a strong correlation (p < 0.05) between the PFAA analytes, potentially indicated the fate of PFAAs in the area's drinking water sources, whereas the hierarchical cluster analysis (HCA) and principal component analysis (PCA) statistics identified industrial, domestic, agricultural, and commercial applications as potential point and non-point sources of PFAA contamination in the area. From risk perspectives, the overall PFAA toxicity in water resources was within the ecological health risk thresholds, where for the human population the hazard quotient (HQ) values of individual PFAAs were < 1, indicating no risk from the drinking water sources; however, the hazard index (HI) from the ∑PFAAs should not be underestimated, as it may significantly result in potential chronic toxicity to exposed adults, followed by children.

Contamination status, partitioning behavior, ecological risks assessment of legacy and emerging per- and polyfluoroalkyl substances in a typical heavily polluted semi-enclosed bay, China.

The contaminant status, spatial distribution, partitioning behavior, and ecological risks of 26 legacy and emerging perfluoroalkyl and polyfluoroalkyl substances (PFASs) in Laizhou Bay, China were investigated. The concentrations of ∑PFASs in surface and bottom seawater ranged from 37.2 to 222 ng/L and from 34.2 to 305 ng/L with an average of 116 ± 62.7 and 138 ± 93.8 ng/L, respectively. There were no significant differences in the average concentrations between the surface and bottom seawater (P > 0.05). Perfluorooctanoic acid (PFOA) and short-chain PFASs dominated the composition of PFASs in seawater. The concentrations of ∑PFASs in sediments ranged from 0.997 to 7.21 ng/g dry weight (dw), dominated by perfluorobutane sulfonate (PFBS), perfluorobutanoic acid (PFBA), and long-chain PFASs. The emerging alternatives of perfluoro-1-butane-sulfonamide (FBSA) and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) were detected for the first time in Laizhou Bay. The ∑PFASs in seawater in the southwest of the bay were higher than those in the northeast of the bay. The ∑PFASs in sediments in the northeast sea area were higher than those in the inner area of the bay. Log Kd and log Koc values increased with increasing carbon chain length for PFASs compounds. Ecological risk assessments indicated a low ecological risk associated with HFPO-DA but a moderate risk associated with PFOA contamination in Laizhou Bay. Positive matrix factorization (PMF) analysis revealed that fluoropolymer manufacturing, metal plating plants, and textile treatments were identified as major sources contributing to PFASs contamination.

Tissue-specific distribution and bioaccumulation of perfluoroalkyl acids, isomers, alternatives, and precursors in citrus trees of contaminated fields: Implication for risk assessment.

The ingestion of fruits containing perfluoroalkyl acids (PFAAs) presents potential hazards to human health. This study aimed to fill knowledge gaps concerning the tissue-specific distribution patterns and bioaccumulation behavior of PFAAs and their isomers, alternatives, and precursors (collectively as per-/polyfluoroalkyl substances, PFASs) within citrus trees growing in contaminated fields. It also assessed the potential contribution of precursor degradation to human exposure risk of PFASs. High concentrations of total target PFASs (∑PFASstarget, 92.45-7496.16 ng/g dw) and precursors measured through the total oxidizable precursor (TOP) assay (130.80-13979.21 ng/g dw) were found in citrus tree tissues, and short-chain PFASs constituted the primary components. The total PFASs concentrations followed the order of leaves > fruits > branches, bark > wood, and peel > pulp > seeds. The average contamination burden of peel (∑PFASstarget: 57.75%; precursors: 71.15%) was highest among fruit tissues. Bioaccumulation factors (BAFs) and translocation potentials of short-chain, branched, or carboxylate-based PFASs exceeded those of their relatively hydrophobic counterparts, while ether-based PFASs showed lower BAFs than similar PFAAs in above-ground tissues of citrus trees. In the risk assessment of residents consuming contaminated citruses, precursor degradation contributed approximately 36.07% to total PFASs exposure, and therefore should not be ignored.

Multi-media distribution and risk assessment of per- and polyfluoroalkyl substances in the Huai River Basin, China.

The widespread existence, environmental persistence, and risks of per- and polyfluoroalkyl substances (PFASs) have attracted widespread attention. Herein, the distribution and risk assessment of PFASs were investigated from the Huai River Basin. The ranges in different media were 29.83-217.96 (average of 75.82 ± 35.64 ng/L) in water, 0.17-9.55 ng/g (2.56 ± 2.83 ng/g) in sediments, and 0.21-9.76 ng/g (3.43 ± 3.07 ng/g) in biota. Perfluoropentanoic acid (PFPeA) was the most prevalent PFAS in surface water, followed by perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), accounted for 42.62 %, 22.23 % and 17.72 % of the total concentrations of the PFASs analyzed, respectively. PFBA was dominant in sediments, accounting for 60.37 % of the total concentrations of the PFASs analyzed. Perfluorooctane sulfonate (PFOS) was the main pollutant in biota, and the highest concentration (5.09 ng/g) was found in Channa argus. Considering the measured concentrations in water, sediments and biota, the sediment-water partition coefficients (log Kd) and bioaccumulation factors (BAF) of PFASs were determined. The log Kd of the PFASs differed among those with a different carbon chain length, C7-C11 PFASs were more likely to be adsorbed onto sediments as the carbon chain length increases, and PFUnDA and PFDA showed the higher BAF value in Channa argus. PFASs in the Huai River Basin posed an acceptable ecological risk, and long-chain PFAS contamination provided green algae with a higher potential ecological risk. Compared to drinking water, aquatic products constituted a higher PFASs threat to human health, especially for children. The highest HQ was found in PFOS, with an HQmax of 0.97-4.32. Residents in the Huai River Basin should reduce their intake of Channa argus, Coilia nasus, and Carassius auratus, children aged 2 to 4 are limited to consuming no more than 6.9 g/d, 9.7 g/d, and 16.6 g/d, respectively.

Per- and polyfluoroalkyl substances (PFAS) in grocery store foods: method optimization, occurrence, and exposure assessment.

Dietary exposure to per- and polyfluoroalkyl substances (PFAS) is poorly understood. Evaluating PFAS in food is complicated by the need to evaluate varied matrices and a lack of a standard, matrix-specific sample extraction methods. Prior food studies implemented universal rather than matrix-specific extraction approaches, which may yield false negatives and an underestimation of PFAS dietary exposure if methods are not suitable to all matrices. Here the objectives were to screen and optimize PFAS extraction methods for plants, tissues, and dairy; apply optimized extraction methods to a grocery store food survey; and compare estimated exposure to published reference doses (RfDs). Optimized, matrix-specific extractions generally yielded internal standard recoveries of 50-150% and matrix spike recoveries of 70-130%. The frequency of PFAS detection in grocery store foods (16 of 22 products) was higher than in previous work. PFAS were detected at concentrations of 10 ng kgdw-1 (perfluorobutane sulfonate; washed green beans and perfluorohexanoic acid; unwashed tomato) to 2680 ng kgdw-1 (perfluorohexane sulfonate; radish). Concentrations of perfluorooctanoic acid (PFOA) in carrots, lettuce, radish, and canned green beans yielded median exposure intake (EI) values of 0.016-0.240 ng per kgbw-day, which exceeded the EPA RfD (0.0015 ng per kgbw-day). Washing reduced radish PFOA concentrations below detection, but EIs at the reporting limit still exceeded the RfD. The combination of improved data quality and greater frequency of PFAS detection vs. prior studies plus EI > RfD for some PFAS suggests a need for matrix-specific extractions and analysis of PFAS in additional grocery store foods from broader geographic regions.

Risk assessment and partitioning behavior of PFASs in environmental matrices from an e-waste recycling area.

OBJECTIVE: Perfluoroalkyl and polyfluoroalkyl substance (PFAS) contamination and their human exposure risks are a major concern. However, knowledge of PFAS contamination in environments near e-waste recycling sites and their health risk assessment are scarce. METHODS: We measured the concentrations of PFASs in soil (n = 12), water (n = 12) and atmospheric samples (n = 26) by LCP-MS/MS, analyzed the source apportionment of PFASs by PCA, and investigated the child health risk assessment from an e-waste recycling area (Guiyu) and a reference area (Haojiang). RESULTS: We found high concentrations of PFASs in the atmosphere and low concentrations of PFASs in soil. The average concentration of perfluoro-n-heptanoic acid (PFHpA) (9.43 ng/L) was highest among PFASs in water. The concentrations PFASs in the atmosphere and water were higher in the e-waste recycling area than in the reference area (p < 0.05). According to Multi-Linear regression model, we found that daily intake doses for PFASs in air of PFODA [ß (95 % CI): -0.217 (-0.332, -0.048), p < 0.05] and PFBS [ß (95 % CI): -0.064 (-0.106, -0.006), p < 0.05] were negatively associated with child BMI. PFBA [ß (95 % CI: -1.039 (-2.454, -0.010), p < 0.05] was negatively correlated with child head circumference. CONCLUSION: The concentrations of PFASs in the water and atmosphere are higher in the e-waste recycling site than in the reference area. We found that their intake affected growth and development in children. We need to reduce pollution from PFASs in the e-waste recycling area while maintaining a focus on their impact on child health.

An integrated assessment of ecological and human health risks of per- and polyfluoroalkyl substances through toxicity prediction approaches.

Per- and polyfluoroalkyl substances (PFAS) are also known as "forever chemicals" due to their persistence and ubiquitous environmental distribution. This review aims to summarize the global PFAS distribution in surface water and identify its ecological and human risks through integrated assessment. Moreover, it provides a holistic insight into the studies highlighting the human biomonitoring and toxicological screening of PFAS in freshwater and marine species using quantitative structure-activity relationship (QSAR) based models. Literature showed that PFOA and PFOS were the most prevalent chemicals found in surface water. The highest PFAS levels were reported in the US, China, and Australia. The TEST model showed relatively low LC50 of PFDA and PFOS for Pimephales promelas (0.36 and 0.91 mg/L) and high bioaccumulation factors (518 and 921), revealing an elevated associated toxicity. The risk quotients (RQs) values for P. promelas and Daphnia magna were found to be 269 and 23.7 for PFOS. Studies confirmed that long-chain PFAS such as PFOS and PFOA undergo bioaccumulation in aquatic organisms and induce toxicological effects such as oxidative stress, transgenerational epigenetic effects, disturbed genetic and enzymatic responses, perturbed immune system, hepatotoxicity, neurobehavioral toxicity, altered genetic and enzymatic responses, and metabolism abnormalities. Human biomonitoring studies found the highest PFOS, PFOA, and PFHxS levels in urine, cerebrospinal fluid, and serum samples. Further, long-chain PFOA and PFOS exposure create severe health implications such as hyperuricemia, reduced birth weight, and immunotoxicity in humans. Molecular docking analysis revealed that short-chain PFBS (-11.84 Kcal/mol) and long-chain PFUnDA (-10.53 Kcal/mol) displayed the strongest binding interactions with human serum albumin protein. Lastly, research challenges and future perspectives for PFAS toxicological implications were also discussed, which helps to mitigate associated pollution and ecological risks.

Human health risk-based soil generic assessment criteria of representative perfluoroalkyl acids (PFAAs) under the agricultural land use in typical Chinese regions.

Perfluoroalkyl acid substances (PFAAs), such as perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS), perfluorooctane acid (PFOA) and perfluoroooctane sulfonic acid (PFOS) are frequently detected in the global environment and can cause potential health hazards even at low levels. In this study, quantitative human health risk assessment was undertaken to derive soil generic assessment criteria (GAC) for four PFAAs under the agricultural land scenario in the evaluated Chinese regions, which considered multiple exposure pathways including vegetables consumption, dermal absorption, ingestion of soil and dust, and exposure from non-soil sources. It is showed that the calculated GAC for four PFAAs in Guangdong and Shandong Provinces were less stringent than those in Zhejiang and Jiangsu Provinces, and Shanghai City, owing to the low exposure from non-soil sources in former two provinces. In addition, GAC of PFOS were the most stringent in the range of 0.28-0.50 µg kg-1 in the studied regions, followed by PFOA (1.36-2.20 µg kg-1), PFBA (42.59-68.03 µg kg-1) and PFBS (474.59-749.60 µg kg-1), mainly attributable to significantly more stringent toxicological values of PFOA and PFOS. Correspondingly, the potential health hazards exist for PFOA in the studied regions except Guangdong Province, and PFOS only in Zhejiang and Jiangsu Provinces as indicated by the hazard quotients ranging from 1.04 to 19.49, but no health hazards are identified for PFBA and PFBS. The dominant exposure pathway was found to be consumption of vegetables and attached soil for PFBA and PFBS, contributing to more than 93% of the total exposure, compared to 49.91-76.69% for PFOA and PFOS due to significant exposure from non-soil sources levels. Overall, this study provides a technical reference on how to derive scientifically justifiable soil GAC for representative PFAAs for maintaining and assessing soil quality and food safety internationally under the agricultural land use.

Legacy and novel perfluoroalkyl substances in major economic species of invertebrates in South China Sea: Health implication from consumption.

Continuously release of perfluoroalkyl substances (PFASs) would pose non-negligible impacts on environment, organisms, and human health. In present study, 18 PFASs in 7 typical economic invertebrates and their habitats were investigated from the South China Sea. The higher concentrations of PFASs in the nearshore water (6.61-15.54 ng/L) and sediment (0.82-8.84 ng/g) obviously due to frequent human activities. Long-chain PFASs have tendency to accumulate in sediment, however, short-chain PFASs dominated in biota. The acute reference dose (%ARfD) and hazard ratios (HR) of major PFASs in biota were all <100 %, and also below 1, respectively, which means that consumption of PFASs from seafood does not pose risk and threat to human health. However, it should be taken into account that the HR of PFHxA in Mimachlamys nobilis reached 0.82. Potential adverse effects toward human health induced by short-chain PFASs (such as <6 C) via invertebrate seafood consumption should be concerned.

Perfluoroalkyl substances in Romanian wastewater treatment plants: Transfer to surface waters, environmental and human risk assessment.

The current study aimed to determine the concentration levels of nine perfluoroalkyl substances (PFAS) in the five most significant Romanian wastewater treatment plants (WWTPs) and their transfer to natural receivers. The analytes were concentrated using a solid-phase extraction/ultrasonic-assisted extraction procedures and then selectively quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS) using electrospray ionization. In most of the wastewater samples investigated, the dominant compounds were perfluoropentanoic acid (PFPeA), perfluorooctanoic acid (PFOA), and perfluorooctansulfonate acid (PFOS), with the maximum concentration range between 105 and 316 ng/L in influents, 14.8-31.3 ng/L in effluents and removal efficiencies higher than 80 % for all selected PFAS compounds. In sewage sludge samples, PFOA and PFOS were the majority substances, with values up to 35.8 ng/g dw for PFOA and 27.8 ng/g dw for PFOS. PFOA and PFOS achieved the maximum levels by estimating mass loading and emission levels. As a result, 237 mg/day/1000 people of PFOA and 95.5 mg/day/1000 people of PFOS are entering daily in the WWTPs, while up to 31 mg/day/1000 people of PFOA and up to 13.6 mg/day/1000 people of PFOS are discharged daily into the natural emissaries. Human risk assessment shows that PFOA and PFOS are low to high risk for all age and gender categories. Children are the most exposed to PFOA and PFOS contamination in drinking water. Environmental risk assessment reveals that PFOA exhibits a low risk for some insect species, PFOS - a low risk for freshwater shrimps and a medium risk for midges, while perfluoroundecanoic acid (PFNuDA) could have a low to medium risk for midges. No assessment studies regarding the environmental and human risk of PFAS have been performed in Romania.

Large-scale assessment of exposure to legacy and emerging per- and polyfluoroalkyl substances in China's shorebirds.

Emerging per- and polyfluoroalkyl substances (PFAS) have become more widely applied, whereas legacy PFAS such as PFOS continue to distribute ubiquitously in the environment. Large-scale assessment of wildlife exposure to both emerging and legacy PFAS plays a key role in effective biomonitoring to better discriminate regional contamination patterns and provide early warnings. Using eggs of two closely-related shorebird species collected across China during the breeding season in 2021, we constructed contrasting PFAS levels and profiles in coastal versus inland populations. The highest ∑PFAS concentrations were found in two Kentish plover (Charadrius alexandrinus) populations from the Bohai Sea, a semi-enclosed shallow bay located in northeast China. These two populations showed exceptionally high PFOA concentrations (mean: 94 and 121 ng/g wet weight; West and North Bohai Sea, respectively) dominating the overall PFAS profile (66% for both). This pattern is characteristic, compared to that of other seabird eggs worldwide. By comparison, PFAS profile in the white-faced plover (Charadrius dealbatus) population at the South China Sea coast was dominated by PFOS (46%), which showed similar levels to those at the North Bohai Sea coast (mean: 29 and 20 ng/g, respectively). PFAS concentrations of Kentish plovers from the remote Qinghai Lake were lower compared to the three coastal populations, and were dominated by PFNA (mean: 2.6 ng/g, 29%) and PFOS (mean: 2.5 ng/g, 27%). None of the eggs analyzed in the present study exceeded estimated toxicity reference values for PFOS or PFOA. Additionally, the emerging 6:2 Cl-PFESA was detected in eggs from all regions, while its concentrations were highest in the Bohai Sea populations, and short-chain PFBS was only detected in the North Bohai Sea population. Our results indicate intensive local emissions of PFOA and emerging PFAS at the Bohai Sea region, and warrant further investigation and monitoring.

[Pollution Characteristics and Health Risk Assessment of Per- and Polyfluoroalkyl Substances and Emerging Alternatives in Road Dust, Shijiazhuang].

Per- and polyfluoroalkyl substances (PFASs, n=22), including emerging alternatives, in dust samples were analyzed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to study their pollution characteristics. These samples were collected from main and minor roads in Shijiazhuang. Some of the roads were located near sewage treatment plants and fire stations. The results showed that PFASs were ubiquitous in the road dust of Shijiazhuang; in particular, hexafluoropropylene oxide dimer acid (HFPO-DA), an alternative, was measured for the first time in China. The total concentrations of PFASs ranged from 2.62 to 137.65 ng·g-1. Perfluorooctanoic acid (PFOA) was the dominant PFAS, followed by perfluorobutanoic acid (PFBA), HFPO-DA, and perfluorooctane sulfonic acid (PFOS). The highest and lowest levels of PFASs were observed in the northwest and southeast regions of Shijiazhuang, respectively. The compositions of PFASs were obviously different in road dust near sewage treatment plants and fire stations, especially for the types of emerging alternatives. Health risk assessment indicated that road dust intake had a low risk of human exposure to PFASs and emerging alternatives. Among the three routes (ingestion intake, inhalation intake, and dermal contact), ingestion intake was the main route for PFASs and emerging alternatives in road dust to enter the human body. Under the same exposure route, the exposure dose of children was higher than that of adults.

Transport and transformation of perfluoroalkyl acids, isomer profiles, novel alternatives and unknown precursors from factories to dinner plates in China: New insights into crop bioaccumulation prediction and risk assessment.

Perfluoroalkyl acids (PFAAs) are contaminants of global concern, and the inadvertent consumption of PFAA-contaminated crops may pose a threat to public health. Therefore, systematically studying their source tracing, bioaccumulation prediction and risk assessments in crops is an urgent priority. This study investigated the source apportionment and transport of PFAAs and novel fluorinated alternatives (collectively as per- and polyfluoroalkyl substances, PFASs) from factories to agricultural fields in a fluorochemical industrial region of China. Furthermore, bioaccumulation specificities and prediction of these chemicals in different vegetables were explored, followed by a comprehensive risk assessment from agricultural fields to dinner plates which considered precursor degradation. A positive matrix factorization model revealed that approximately 70 % of PFASs in agricultural soils were derived from fluorochemical manufacturing and metal processing. Alarming levels of ∑PFASs ranged 8.28-84.3 ng/g in soils and 163-7176 ng/g in vegetables. PFAS with short carbon chain or carboxylic acid group as well as branched isomers exhibited higher environmental transport potentials and bioaccumulation factors (BAFs) across a range of vegetables. The BAFs of different isomers of perfluorooctanoic acid (PFOA) decreased as the perfluoromethyl group moved further from the acid functional group. Hexafluoropropylene oxide dimer acid (GenX) showed relatively low BAFs, probably related to its ether bond with a high affinity to soil. Vegetables with fewer Casparian strips (e.g., carrot and radish), or more protein, possessed larger BAFs of PFASs. A bioaccumulation equation integrating critical parameters of PFASs, vegetables and soils, was built and corroborated with a good contamination prediction. After a total oxidizable precursors (TOP) assay, incremental perfluoroalkyl carboxylic acids (PFCAs) were massively found (325-5940 ng/g) in edible vegetable parts. Besides, precursor degradation and volatilization loss of PFASs was firstly confirmed during vegetable cooking. A risk assessment based on the TOP assay was developed to assist the protection of vegetable consumers.

Perfluoroalkyl acids in the aquatic environment of a fluorine industry-impacted region: Spatiotemporal distribution, partition behavior, source, and risk assessment.

The present study investigated the temporal and spatial distributions, partition behaviors, sources, and risks of 14 perfluoroalkyl acids (PFAAs) in the aquatic environment of a fluorine industry-impacted region. The total concentrations of 14 PFAAs (ΣPFAAs) were 118.10-2235.4 ng/L, 40.00-2316.1 ng/g dw, and 6.90-180.5 ng/g dw in dissolved, suspended particle matter (SPM), and sedimentary phases, respectively. The predominant pollutants in the dissolved and SPM phases were perfluoroalkyl carboxylic acids (PFCAs) with carbon chain lengths <9, whereas C13 and C14 PFCAs accounted for a large proportion in the sedimentary phase. The dry season exhibited the highest concentration of ΣPFAAs in the dissolved phase (500.9 ± 350.2 ng/L), while the wet season showed the highest concentrations of ΣPFAAs in the SPM and sedimentary phases (591.6 ± 469.1 ng/g dw and 59.7 ± 35.5 ng/g dw, respectively). Significantly higher concentrations of PFAAs have been found in sewage plant and industrial areas. The concentration of PFAAs in the Xupu water source area (XPS) was slightly higher than that in other water source areas of the Yangtze River, which were either not affected or were less affected by the fluorine industry. The log KD-SPM (distribution coefficient between SPM and water), log KD-SED (distribution coefficient between sediment and water), and log KOC-SED (the organic carbon normalized distribution coefficient) of PFAAs showed significant differences between the wet season and dry season, which may also be affected by carbon chain length. Source identification results showed that industries, wastewater discharge, and nonpoint sources were the main sources of PFAAs in this region. The ecological risk posed by long-chain PFAAs in aquatic organisms cannot be ignored, especially in areas with intensive industrial and agricultural activities. Health risks may exist for local toddlers with long-term exposure to perfluorooctanoic acid (PFOA) through drinking water intake and dermal contact.

Exposure and Health Risk Assessment of Per- and Polyfluoroalkyl Substances in Crayfish from the Middle and Lower Reaches of the Yangtze River.

Per- and polyfluoroalkyl substances (PFASs) are a novel class of emerging persistent organic pollutants (POPs) owing to their environmental persistence and bioaccumulation. Red swamp crayfish is a major source of exposure to PFASs, while the dietary intake of PFASs from crayfish is still unclear. We investigated the concentrations of PFASs in 130 batches of crayfish and 100 environmental samples from Middle and Lower Reaches of the Yangtze River Delta. Seven Perfluoroalkyl carboxylic acids (PFCAs), 3 Perfluoroalkyl sulfonates (PFSAs), and 6:2 Cl-PFESA were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Meanwhile, PFASs exposure levels were examined concretely in four tissues of crayfish and different circulation links. The average daily intake (ADI) risk model was used to evaluate the human health risk of consuming crayfish and suggested that the risk of PFASs exposure is at a low level.

Toxicity of Per- and Polyfluoroalkyl Substances to Aquatic Invertebrates, Planktons, and Microorganisms.

Per- and polyfluoroalkyl substances (PFASs), recognized worldwide as emerging pollutants, may pose a substantial threat to human health and our environment due to their stability, high concentrations, wide distribution, and easy accumulation. Ever since perfluorooctane sulfonate and perfluorooctanoic acid were recognized by the Stockholm Convention on Persistent Organic Pollutants, the public has become increasingly concerned about potential contamination and the environmental risks associated with PFASs. Ubiquitous PFAS contamination of drinking water, groundwater, surface water, and sediment has been detected, especially in areas with rapid industrial and economic development. Its accumulation in living organisms and foods has accentuated the importance of investigations into aquatic organisms at the bottom of the food chain, as the stability and integrity of the food web as well as the population quantity and structure of the aquatic ecosystem may be affected. This review provides a comprehensive summary of the toxic and toxicity-related effects of PFASs on aquatic plankton, aquatic invertebrates and microorganisms, the characteristics of different target aquatic organisms in toxicity investigations, and a feasibility evaluation of PFAS substitutes to provide valuable suggestions for further utilization and regulation of PFASs and their substitutes.

Occurrence, fate and risk assessment of per- and polyfluoroalkyl substances in wastewater treatment plants in Shaanxi, China.

Wastewater treatment plants (WWTPs) are considered as major sinks for per- and polyfluoroalkyl substances (PFASs). However, conventional WWTPs with low efficiency are also a secondary point source of PFASs entering the environment. Herein, a large-scale investigation of PFASs was conducted in 44 WWTPs throughout Shaanxi Province in the transitional zone between North and South China. The composition profiles of target PFASs differed between wastewater and sludge samples. Perfluorobutanoic acid was dominant in wastewater influent and effluent samples, with maximum concentrations of 59.8 and 11.4 ng/L, respectively. Perfluorooctane sulfonic acid occurred predominantly in sludge samples, with a maximum concentration of 73.2 ng/g. Through wastewater treatment, short-chain PFASs with an even number of carbon atoms were mostly removed, whereas short-chain PFASs with an odd number of carbon atoms were primarily discharged into receiving water. Long-chain PFASs (perfluoroalkyl carboxylic acids: C ≥ 8; perfluoroalkane sulfonic acids: C ≥ 6) were not removed efficiently and secondary production might occur during treatment. Based on the risk quotient, PFASs residues in wastewater effluent posed minimal ecological risk, but the residues in sludge posed low to high potential risk. The mass loadings of PFASs discharged through wastewater and sludge were 15.5 and 3.74 kg/year, respectively, from all WWTPs in Shaanxi Province.

Assessment of perfluorohexane sulfonic acid (PFHxS)-related compounds degradation potential: Computational and experimental approaches.

Perfluorohexane sulfonic acid (PFHxS) and PFHxS-related compounds are listed in Annex A of the Stockholm Convention without specific exemptions. Substances that potentially degrade to PFHxS are considered as their related compounds. Unfortunately, the degradation behavior of PFHxS precursors, an important basis for the corresponding chemical regulation, remains unclear. Herein, based on the hypothesis that bond dissociation enthalpy (BDE) is the determining factor for the degradation of PFHxS precursors, the BDE of PFHxS-related precursors to produceC6F13SO2-groups was calculated. In addition, quantitative structure-activity relationship models based on partial least squares, partial least squares discrimination analysis, and support vector machine algorithms were developed to predict the BDE of 48 PFHxS precursors and distinguish the precursors with different degradation potential. Subsequent photodegradation experiments demonstrated that the order of degradation rates was consistent with that predicted by theoretical models. Importantly, perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid, and not PFHxS, were detected as the degradation products of potential PFHxS precursors. Sulfonamides, phenyl unit, and other radicals in the non-nucleus part of PFHxS precursors were identified as the critical molecular segments that affect their degradation potential. Ultimately, by comparing BDE values, it was theoretically speculated that PFHxS related compounds exhibit a greater potential to generate PFHxA than PFHxS. Results in this study indicated for the first time that not all the compounds containing C6F13SO2- groups were guaranteed to degrade into PFHxS under natural conditions.