Occurrence,Spatial Distribution,Sources and Risk Assessment of Per-and Polyfluoroalkyl Substances in Surface Sediments of the Yellow River Delta Wetland

Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence,spatial distribution,potential sources,and ecological risks of PFASs.Twenty-three out of 26 targeted PFASs were detected in surface sediment samples from the YRDW,with totalΣ23PFASs concentrations ranging from 0.23 to 16.30 ng g^(-1) dw and a median value of 2.27 ng g^(-1) dw.Perfluorooctanoic acid(PFOA),perfluorobutanoic acid(PFBA)and perfluorooctanesulfonic acid(PFOS)were the main contaminants.The detection frequency and concentration of perfluoroalkyl carboxylic acids(PFCAs)were higher than those of perfluoroal-kanesulfonic acids(PFSAs),while those of long-chain PFASs were higher than those of short-chain PFASs.The emerging PFASs substitutes were dominated by 6:2 chlorinated polyfluoroalkyl ether sulfonic acid(6:2 Cl-PFESA).The distribution of PFASs is significantly influenced by the total organic carbon content in the sediments.The concentration of PFASs seems to be related to human activities,with high concentration levels of PFASs near locations such as beaches and villages.By using a positive matrix factorization model,the potential sources of PFASs in the region were identified as metal plating mist inhibitor and fluoropolymer manufacturing sources,metal plating industry and firefighting foam and textile treatment sources,and food packaging material sources.The risk assessment indicated that PFASs in YRDW sediments do not pose a significant ecological risk to benthic organisms in the region overall,but PFOA and PFOS exert a low to moderate risk at individual stations.

Distribution of per-and polyfluoroalkyl substances in blood,serum,and urine of patients with liver cancer and associations with liver function biomarkers

Studies have shown that per-and polyfluoroalkyl substances(PFASs)may be hepatotoxic in animals or humans.However,data on clinical epidemiology are very limited.In this study,21PFASs were determined in patients with liver diseases,with the highest median concentrations detected in the serum sample(26.7 ng/mL),followed by blood(10.7 ng/mL)and urine(5.02 ng/mL).Higher total PFAS concentrations were found in hepatocellular carcinoma(HCC)patients compared to non-HCC patients,with significant discrepancies in serum and blood samples.Besides,significant correlations were also found among PFAS concentrations and age,gender,body mass index(BMI),and liver function biomarkers levels.For example,PFAS concentrations are significantly higher in males than in females;Several serum PFASs concentrations increase with age and BMI,while the serum perfluorohexane sulfonic acid(PFHxS)concentrations are negatively correlated with age.In addition,multiple regression models adjusted for age,gender and BMI found that increased serum perfluorobutane sulfonic acid(PFBS),perfluoroheptane sulfonic acid(PFHpS)and perfluorohexylphosphonic acid(PFHxPA)conentrations are correlated with elevated alkaline phosphatase(ALP),aspartate aminotransferase(AST),and alpha-fetoprotein(AFP)(p<0.05).Our results provide epidemiological support for the future study on the potential clinical hepatotoxicity of PFAS.

Emergency of per-and polyfluoroalkyl substances in drinking water:Status,regulation,and mitigation strategies in developing countries

The detection of per-and polyfluoroalkyl substances(PFAS)in water presents a significant challenge for developing countries,requiring urgent attention.This review focuses on understanding the emergence of PFAS in drinking water,health concerns,and removal strategies for PFAS in water systems in developing countries.This review indicates the need for more studies to be conducted in many developing nations due to limited information on the environmental status and fate of PFAS.The health consequences of PFAS in water are enormous and cannot be overemphasized.Efforts are ongoing to legislate a national standard for PFAS in drinking water.Currently,there are few known mitigation efforts from African countries,in contrast to several developing nations in Asia.Therefore,there is an urgent need to develop economically viable techniques that could be integrated into largescale operations to remove PFAS from water systems in the region.However,despite the success achieved with removing long-chain PFAS from water,more studies are required on strategies for eliminating short-chain moieties in water.

Interaction and combined toxicity of microplastics and per-and polyfluoroalkyl substances in aquatic environment

Microplastics(MPs)are recognized as vectors for the transport of organic contaminants in aquatic environments in addition to their own adverse effects on aquatic organisms.Per-and polyfluoroalkyl substances(PFASs)are widely present in aquatic environments due to their widespread applications,and thus coexist with MPs.Therefore,we focus on the interaction of MPs and PFASs and related combined toxicity in aquatic environments in this work The adsorption of PFASs on MPs is critically reviewed,and new mechanisms such as halogen bonding,π-πinteraction,cation-πinteractions,and micelle formation are proposed.Moreover,the effect of MPs on the transport and transformation of PFASs in aquatic environments is discussed.Based on four typical aquatic organisms(shellfish,Daphnia,algae,and fish),the toxicity of MPs and/or PFASs at the organismal or molecular levels is also evaluated and summarized.Finally,challenges and research perspectives are proposed,and the roles of the shapes and aging process of MPs on PFAS biogeochemical processes and toxicity,especially on PFAS substitutes,are recommended for further investigation.This review provides a better understanding of the interactions and toxic effects of coexisting MPs and PFASs in aquatic environments.

The occurrence of per-and polyfluoroalkyl substances(PFASs) in fluoropolymer raw materials and products made in China

Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.

Temporal trends of per-and polyfluoroalkyl substances(PFAS)in the influent of two of the largest wastewater treatment plants in Australia

Per-and polyfluoroalkyl substances(PFAS)are found ubiquitously in wastewater treatment plants(WWTPs)due to their multiple sources in industry and consumer products.In Australia,limited spatial data are available on PFAS levels inWWTPs influent,while no temporal data have been reported.The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia(WWTP A and B)over a four-year period.Daily influent samples were collected over one week at different seasons from 2014 to 2017.Eleven perfluoroalkyl acids(PFAA)(i.e.seven perfluoroalkyl carboxylic acids(PFCAs)and four perfluoroalkyl sulfonic acids(PFSA))were detected with mean S11PFAA concentrations of 57±3.3e94±17 ng/L at WWTP A,and 31±6.1e142±73 ng/L at WWTP B.The highest mean concentrations were observed for perfluorohexanoate(PFHxA)(20±2 ng/L)in WWTP A,and perfluorooctane sulfonate(PFOS)(17±13 ng/L)in WWTP B.The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017,with mean concentrations of 37±18e138±51 ng/L for WWTP A and 8.8±4.5e29±5.1 ng/L for WWTP B.Higher concentration of 6:2 FTS(1.8e11 folds)than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment.Temporal trends(annual and seasonal)in per-capita mass load were observed for some PFAA,increasing for PFPeA,PFHxA,PFHpA,PFNA,and PFHxS,while decreasing for PFBS and PFOS in either WWTPs.Notably,elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 mg/day/inhabitant.For some PFAS release trends,longer sampling periods would be required to achieve acceptable statistical power.

Diffusive gradients in thin films(DGT) probe for effectively sampling of per-and polyfluoroalkyl substances in waters and sediments

The passive sampling technique, diffusive gradients in thin films(DGT) has attracted increasing interests as an in-situ sampler for organic contaminants including per-and polyfluoroalkyl substances(PFAS). However, its effectiveness has been questioned because of the small effective sampling area(3.1 cm^(2)). In this study, we developed a DGT probe for rapid sampling of eight PFAS in waters and applied it to a water-sediment system. It has a much larger sampling area(27 cm^(2)) and as a result lower method quantification limits(0.15 –0.21 ng/L for one-day deployment and 0.02 – 0.03 ng/L for one-week deployment) and much higher(by > 10 factors) sampling rate(100 m L/day) compared to the standard DGT(piston configuration). The sampler could linearly accumulate PFAS from wastewater, was sensitive enough even for a 24 hr deployment with performance comparable to grab sampling(500m L). The DGT probe provided homogeneous sampling performance along the large exposure area. The use of the probe to investigate distributions of dissolved PFAS around the sediment-water interface was demonstrated. This work, for the first time, demonstrated that the DGT probe is a promising monitoring tool for trace levels of PFAS and a research tool for studying their distribution, migration, and fate in aquatic environments including the sediment-water interface.

北方某典型活动区地下水中PBDEs/PFASs的污染特征

地下水水源中持久性有机污染物的污染将直接威胁人体健康,已成为地下水安全的重点问题之一。选择典型农业活动区天津市某区重要蔬菜种植基地,研究该区地下水中多溴联苯醚(PBDEs)和全氟类化合物(PFASs)的污染分布及其特征,并评价潜在风险。结果表明,该区地下水中PBDEs浓度水平为0~33.71 ng/L(平均浓度为5.43 ng/L),而土壤中PBDEs平均浓度(10.34 ng/g d.w.)高于地下水,存在PBDEs随降雨等条件由土壤渗入地下水的风险。地下水中75%检出BDE-209(十溴联苯醚),推测该区受高溴代阻燃剂产品污染为主。该区地下水中总PFASs浓度为0.321~8.284 ng/L(平均浓度2.413 ng/L),且10类PFASs均有检出,其中以短碳链的全氟辛烷磺酸(PFOS)(0~2.38 ng/L)和长碳链全氟辛酸(PFOA)(0.025~3.94 ng/L)为主。

新型全氟和多氟烷醚类化合物的环境分布与毒性研究进展

全氟和多氟烷基化合物(PFASs)是一类应用广泛的有机物,传统PFASs的代表性化合物包括全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)等。PFOS和PFOA因环境持久性、生物累积性和多种潜在毒性已被《斯德哥尔摩国际公约》列入禁用和限用名录,从而催生了全氟和多氟烷醚类化合物(PFPEs)等替代品的研发应用。近年来,多种PFPEs替代品在人体及饮用水中被频繁检出,引起环境科学界对其安全性的关注。笔者综述了PFPEs的主要类型、环境介质分布和生物毒性等的最新研究进展,并展望了其安全性研究中有待解决的问题。

Non-conventional sorption materials for the removal of legacy and emerging PFAS from water:A review

Per-and polyfluoroalkyl substances(PFAS)are a class of ubiquitous,persistent,and hazardous pollutants that raise concerns for human health and the environment.Typically,PFAS removal from water relies on adsorption techniques using conventional sorption materials like activated carbons(ACs)and ion exchange resins(IERs).However,there is a continuous search for more efficient and performing adsorbent materials to better address the wide range of chemical structures of PFAS in the environment,to increase their selectivity,and to achieve an overall high adsorption capacity and faster uptake kinetics.In this context,results from the application of non-conventional sorption materials(i.e.,readily available biological-based materials like proteins and advanced materials like nanocomposites and cyclodextrins)are reported and discussed in consideration of the following criteria:i)removal efficiency and kinetics of legacy PFAS(e.g.,PFOA,PFBA)as well as newly-introduced and emerging PFAS(e.g.,GenX),ii)representativity of environmental conditions in the experimental setup(e.g.,use of environmentally relevant experimental concentrations),iii)regenerability,reusability and applicability of the materials,and iv)role of the material modifications on PFAS adsorption.From this review,it emerged that organic frameworks,nano(ligno)cellulosic-based materials,and layered double hydroxides are among the most promising materials herein investigated for PFAS adsorption,and it was also observed that the presence of fluorine-and amine-moieties in the material structure improve both the selectivity and PFAS uptake.However,the lack of data on their applicability in real environments and the costs involved means that this research is still in its infancy and need further investigation.

Gestational PFAS exposure and newborn size:The modifying effect of cord blood fatty acids

Per-and polyfluoroalkyl substances(PFASs)can disrupt lipid metabolism,and changes in cord blood fatty acid composition have been observed in small newborns.Emerging evidence suggests that exposure to PFASs during pregnancy is linked to decreased newborn size,although the evidence is not consistent.The modifying effect of fatty acids on the associations of gestational PFAS exposure with newborn size is still unknown.Here we show that the nutritional status of the fetus,as indicated by the level of fatty acids in the cord blood,mitigates the adverse effects of gestational PFAS exposure on the size of the newborn.Our study confirms the adverse developmental effects of PFASs and identifies emerging short-chain PFASs as the primary drivers of reduced newborn size,despite their lower exposure burden compared to legacy PFASs.Additionally,we find the protective role of cord blood fatty acids,suggesting potential strategies for mitigating the detrimental effects of emerging environmental exposures on human health.Our findings provide new evidence of the potential toxicity of emerging PFASs and call for further toxicity evaluations of these pollutants for regulatory purposes.Future studies should consider the complex interaction between exposure and nutrition within the human body,particularly during the first thousand days of life,to promote lifelong health.

Influence of microplastics on the photodegradation of perfluorooctane sulfonamide (FOSA)

PFAS(per-and polyfluoroalkyl substances)are omnipresent in the environment and their transportation and transformation have attracted increased attention.Microplastics are another potential risk substances that can serve as a carrier for ubiquitous pollutants,thus affecting the presence of PFAS in the environment.In this study,the adsorption of perfluorooctane sulfonamide(FOSA)and perfluorooctanoic acid(PFOA)on four microplastics(PE,PVC,PS,and PTFE)and their effect on the photodegradation of FOSA were studied.The adsorption capacity of FOSA by PS was the highest,in similar,PS displayed the highest adsorption capacity in the presence of PFOA.Different effects of pH and salinity on the adsorption of FOSA and PFOA were observed among different microplastics indicating inconsistent interaction mechanisms.Furthermore,FOSA could be photodegraded,with PFOA as the main product,while the presence of microplastics had a negligible effect on the degradation of this contaminant.The results indicated that microplastics could act as PFAS concentrators.Moreover,their photochemical inertiasmake the pollutants enriched onmicroplastics more resistant to degradation.

Recent Advances in the Analytical Techniques for PFASs and Corresponding Intermediates During Their Chemical Decomposition

Per-and polyfluoroalkyl substances(PFASs)have been restricted from production and consumption in many countries due to their persistence and biological toxicity.With the development of removal technologies,the requirement on the detection of different kinds of PFASs and their derivates is increasing.A suitable analytical method is the prerequisite and basis for the study of the degradation of PFASs.As various analytical methods have been reported,questions about which one is more suitable have arisen.It is a right time to summarize the past and suggest the future.In this paper,we summarized and discussed the analytical methods applied in the chemical degradation of PFASs.We also proposed the current problems and discussed the future directions in this field.