Long-chain Polyfluoroalkyl Substances Research Articles

Recent Methods of Effectively Removing Long-chain and Short-chain Per- and Poly-fluoroalkyl Substances from Drinking Water

As a persistent organic pollutant, the non-biodegradable per- and poly-fluoroalkyl substances (PFAS) pervade an extensive scope of life, leading to widespread contamination of water resources including drinking water. Correlated with multiple diseases, PFAS is highly correlated with dyslipidemia. While the production of long-chain PFAS is banned, many short-chain PFAS become the alternatives. Although most short-chain alternatives show less hazard, some may possess greater harm. As a result, the removal of PFAS from drinking becomes urgent. This paper reviewed the recent methods of adsorptive removal of PFAS by activated carbon, ion exchange resins, and metal-organic frameworks. The main mechanism and innovative modifications of each adsorptive material are summarized, and both long-chain and short-chain PFAS are discussed in each section. This study aims to provide a basic understanding of the current removal approaches of PFAS for scholars. Through literature review, activated carbon and metal-organic framework remain highly effective with evident mechanisms for adsorbing long-chain PAFS, while ion exchange resins show considerable potential in adsorbing short-chain and ultrashort-chain PFAS.

Reproductive toxicity of perfluorobutane sulfonate in zebrafish (Danio rerio): Impacts on oxidative stress, hormone disruption and HPGL axis dysregulation.

Per and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals extensively used in consumer products. Perfluorobutane sulfonate (PFBS), a short-chain PFAS, has been introduced as an alternative to long-chain PFAS, but limited studies have investigated its reproductive toxicity in fish. In this study, adult zebrafish were exposed to PFBS at concentrations of 0.14, 1.4, and 14 μM for 28 days. PFBS accumulation in male and female gonads was confirmed by specific mass spectrum peaks detected in exposed samples. PFBS exposure at 14 μM significantly reduced egg production and hatching rates. The gonadosomatic index (GSI) was decreased by 73 % in males and 50 % in females compared to the control. PFBS impaired antioxidant enzyme activity, with superoxide dismutase (SOD) 4.73 U/mg protein in testes and 3.46 U/mg protein in ovaries, leading to elevated lipid peroxidation and nitric oxide levels in males (0.053 μmol/mg/ml and 5.65 μM) and females (0.047 μmol/mg/ml and 4.01 μM), respectively. PFBS exposure induced endocrine disruption through the hypothalamic-pituitary-gonadal-liver (HPGL) axis, showing increased estrogen (50 pg/g) in males and testosterone (181.6 pg/g) in females. Gene expression analysis revealed significant alteration in the HPGL axis, including cyp19b, er2b, fshb, lhb, 17βhsd, lhr, cyp19a, and vtg, indicating PFBS influence on sex hormone synthesis. Histopathological analysis of PFBS exposure groups revealed a reduction of spermatozoa in the testes and late vitellogenic oocytes in the ovaries. Overall, the result of the present study indicates that PFBS exposure induces oxidative stress, disrupts hormone synthesis, dysregulates HPGL axis gene expression, and causes reproductive toxicity in both male and female zebrafish.

New Insights into Thermal Degradation Products of Long-Chain Per- and Polyfluoroalkyl Substances (PFAS) and Their Mineralization Enhancement Using Additives.

The products of incomplete destruction (PIDs) of per- and polyfluoroalkyl substances (PFAS) represent a substantial ambiguity when employing thermal treatments to remediate PFAS-contaminated materials. In this study, we present new information on PIDs produced in both inert and oxidative environments from five long-chain PFAS, including three now regulated under the U.S. Safe Drinking Water Act, one cationic precursor compound, and one C10 PFAS. The data did not support the generation of tetrafluoromethane from any of the studied PFAS, and carbonyl fluoride was found only from potassium perfluorooctanesulfonate (K-PFOS) when heated in air in a narrow temperature range. Oxidative conditions (air) were observed to facilitate PFAS thermal degradation and accelerate the mineralization of K-PFOS. Spectroscopic data suggest that PFAS thermal degradation is initiated by the cleavage of bonds that form perfluoroalkyl radicals, leading to organofluorine PIDs (e.g., perfluoroalkenes). In air, perfluoroalkyl radicals react with oxygen to form oxygen-containing PIDs. The mineralization of PFAS was enhanced by adding solid additives, which were categorized as highly effective (e.g., granular activated carbon (GAC) and certain noble metals), moderately effective, and noneffective. Remarkably, simply by adding GAC, we achieved >90% mineralization of perfluorooctanoic acid at 300 °C and ∼1.9 atm within just 60 min without using water or solvents.

Toxic layering and compound extremes: Per- and polyfluoroalkyl substances (PFAS) exposure in rural, environmental justice copper mining communities

Per- and polyfluoroalkyl substances (PFAS) are pervasive environmental pollutants with significant impacts on ecosystems and public health. This study aimed to characterize PFAS concentrations in an environmental justice community impacted by active/legacy copper mining, compounded by wildfires and flash floods. Additionally, the study explored the (re)mobilization of PFAS and co-occurrence with metal(loid)s following these events. Twenty-eight PFAS compounds in 35 residential and 8 control surface soil samples were analyzed via liquid chromatography-tandem mass spectrometry (LCMS/MS). The maximum total PFAS concentration observed in the residential samples was 96.40 μg kg−1, compared to 1.69 μgkg−1 in the control samples. Perfluorobutanoic acid (PFBA) had a maximum concentration of 61 μg kg−1 in residential samples, while Perfluorohexane sulfonic acid (PFHxS) had the highest concentration in the control samples at 0.92 μg kg−1. Long-chain PFAS were most dominant in this study. Perfluorooctane sulfonic acid (PFOS) (58 % of the samples), Perfluorooctanoic acid (PFOA) (35 %), and Perfluorohexane sulfonic acid (PFHxS) (72 %) exceeded the U.S. EPA Soil-to-Groundwater Risk-Based Screening Levels, highlighting the potential risk of contaminants migrating from soil to groundwater, which could ultimately impact groundwater quality. Co-occurrence analysis showed that increases in PFAS concentrations were positively associated with Zn (β = 1.25, p = 0.0034) and Ba (β = 1.23, p = 0.0284) but negatively associated with Pb (β = −0.83, p = 0.0115) and Co (β = −1.38, p = 0.04671). In general, a spatial distribution map indicated that greater PFAS concentrations were observed near potential sources i.e., active mines. This evidence combined with select metal co-occurrence highlights the potential role of mining activities on PFAS concentration.

Diversity, composition, and assembly processes of bacterial communities within per- and polyfluoroalkyl substances (PFAS)-contained urban lake sediments

Per- and polyfluoroalkyl substances (PFAS) are widespread, highly persistent, and bio-accumulative compounds that are increasingly found in the sediments of aquatic systems. Given this accumulation and concerns regarding the environmental impacts of PFAS, their influence on sedimentary bacterial communities remains inadequately studied. Here, we investigated the concentrations of 17 PFAS in sediments from six urban lakes in Nanjing, China, and assessed their effects on the diversity, composition, potential interactions, and assembly mechanisms of sedimentary bacterial communities. Sediment concentrations of PFAS ranged from 4.70 to 5.28 ng·g−1 dry weight. The high concentrations of the short-chain perfluorobutanesulfonic acid (PFBS) suggested its substitution for the long-chain perfluorooctanesulfonic acid (PFOS). As alternatives to long-chain PFAS, short-chain PFAS had similar effects on bacterial communities. The short-chain perfluoropentanoic acid (PFPeA) and the long-chain perfluorotridecanoic acid (PFTrDA) were the most important PFAS related to the ecological patterns of the co-occurrence network and may alter the composition of the sedimentary bacterial communities in the urban lakes. The Anaerolineaceae family represented as keystone bacteria within the PFAS-affected bacterial co-occurrence network. Deterministic processes (65.9 %), particularly homogeneous selection (63.2 %), were the dominant process driving bacterial community assembly. PFAS promoted the phylogenetic clustering and influenced the community dispersal capabilities to shape bacterial community assembly. This study provides a comprehensive analysis of PFAS distribution in sediments across six urban lakes in Nanjing and provides novel insights into the effects of PFAS on sedimentary bacterial communities. Further research is required to elucidate the mechanisms underlying the impacts of PFAS on microbial communities and to evaluate their broader ecological consequences.

Maternal transfer and sex-differences in brain bioaccumulation for Northern bobwhite quail (Colinus virginianus) exposed to per- and poly-fluoroalkyl substances

Per- and poly-fluoroalkyl substances (PFAS) are highly persistent chemicals commonly found in surface protectants, and class B aqueous film forming foams (AFFF), and many other consumer and industrial products. As a result of their widespread application and use, PFAS are now found in environmental media across the globe. Research has revealed that exposure to environmentally relevant concentrations of PFAS can reduce reproductive success and have immunological effects in laboratory animals, including birds. Further, PFAS can be passed down from parents to offspring, posing a threat to sensitive life stages. PFAS may enter the brain by disrupting tight junctions or binding to transporters, but our overall understanding of the interactions and accumulation of PFAS in the avian brain is limited due to the lack of data. We obtained archived samples of male-female pairs of Northern bobwhite quail (NBWQ) from chronic toxicity studies where adults were exposed to either individual PFAS or binary mixtures through drinking water for at least 60 days. PFAS were detected in the brains of exposed adult quail, while brains from control birds had only occasional detections of PFAS; mostly perfluorooctane sulfonic acid (PFOS), likely because our source of birds was pen-raised animals and many PFAS are ubiquitous. Despite similar average daily intake (ADI) for both males and females, we observed higher concentrations of most PFAS in the brains of male birds compared to female birds, with the exception of perfluoroheptanoic acid (PFHpA). For the binary mixture exposures, PFOS appeared to reduce brain concentrations of perfluorohexane sulfonic acid (PFHxS) in both males and females to levels that could not be explained by ADI differences alone. Collectively, study results demonstrated that brain accumulation of short-chain PFAS in birds was not significantly affected by sex, however, long-chain PFAS exposure resulted in avian brain accumulation with generally higher PFAS concentrations in males compared to females. The findings of this study offer insights into the accumulation of PFAS in the avian brain and suggest that there may be sex differences in potential risks associated with exposure to these pervasive chemicals.

Electrifying PFAS Cleanup: Remediation of per- and Polyfluoroalkyl Substances (PFAS) from Water Using Electrosorption and Electrooxidation Techniques

Per- and polyfluoroalkyl substances (PFAS) are a class of man-made chemicals extensively utilized in various industrial applications, including the production of waterproof coatings, non-stick surfaces, surfactants, and firefighting agents. The pervasive use of PFAS has led to their widespread dissemination into the environment, where they are commonly detected in soil, groundwater, drinking water sources, and even remote regions such as Antarctic snow. Recent toxicological investigations have elucidated the propensity of PFAS to bioaccumulate within biological systems, thereby posing significant health risks to both humans and wildlife. Despite advancements in water treatment methodologies, the elimination of PFAS remains a formidable challenge due to their resistance to chemical and biological degradation conferred by their strong carbon-fluorine (C-F) bonds, which render traditional degradation approaches energy-intensive (~108 kWh/g). Thus, effective remediation of PFAS from aqueous matrices is a pressing challenge which requires thoughtful design of materials and scalable systems. Electrochemically driven techniques offer promising avenues for modular and energy efficient PFAS capture and destruction.In this study, we investigated the electrosorption of PFAS using functionalized redox-active copolymer electrodes with 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) groups. Our investigation demonstrated the feasibility of employing oxidizing or reducing potentials to effectuate the capture or release of PFAS via a switch-like mechanism. By tailoring the structural properties of the copolymers to optimize electrostatic and affinity interactions, a notable enhancement in separation efficiency towards hydrophilic short-chain PFAS was achieved. Specifically, the introduction of selective fluorophilic interactions within the redox copolymer structure facilitated the enhanced capture of short-chain PFAS, while the inherent hydrophobicity of the TEMPO copolymer sufficed to drive long-chain PFAS capture via electrostatic interactions. Notably, our research showcases the potential for PFAS capture under environmentally relevant conditions without using additional chemical agents for sorbent regeneration. This was achieved through electro-assisted regeneration upon reduction of the electrode, with a regeneration efficiency of at least 80% observed. Furthermore, we explored the synergistic integration of electrosorption with electrooxidation as a viable strategy for in-situ PFAS eradication from wastewater post-capture.

Application of coniferous bark as sorbent material for per- and polyfluoroalkyl substances – A case study in Sweden

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic contaminants commonly found in drainage water from waste management facilities. Within the European Union, these facilities either treat the water locally or transfer it to wastewater treatment plants to reduce harmful emissions. However, PFAS are a broad class of compounds with varying physicochemical properties, leading to different removal efficiencies for adsorbents. Activated carbon and ion exchange resins are effective but costly, and they can become saturated with other contaminants. Therefore, this study aims to explore inexpensive, abundant alternatives for reducing PFAS concentrations in the environment. In Sweden, bark is a by-product of forestry activities, primarily used as fuel in heat and power plants. This study evaluates the ability of pine and spruce bark to remove PFAS from contaminated drainage water. Initial laboratory experiments employed liquid-to-solid ratios of 10 and 20 to assess the performance of both materials. Results indicated that pine bark exhibited better removal efficiencies, particularly when a layered column with pine bark followed by spruce bark was utilized. The overall removal efficiencies for short-chain PFAS (perfluorinated carbons: PFCA C3–C6 and PFSA C4–C5) and long-chain PFAS (PFCA > C7 and PFSA > C6) were below 20%, except for perfluorooctane sulfonic acid (PFOS), which showed reductions of 40%–80%. The pH of the treated water decreased from 7 to 4 (pine bark) and 5 (spruce bark) after treatment. In a larger-scale trial, a combination of 50% pine bark and 50% spruce bark was tested, achieving similar reductions for PFOS. Although the removal efficiencies were insufficient for exclusive treatment, these materials may be useful in specific applications targeting long-chain PFAS or in conjunction with other treatment methods.

µ-X-ray fluorescence (XRF) and fluorine K-edge µ-X-ray absorption near-edge structure (XANES) spectroscopy for detection of PFAS distribution in the impacted concrete

An improved understanding of the distribution of per- and polyfluoroalkyl substances (PFAS) in PFAS-impacted concrete is important for risk management and decontamination of PFAS. This study incorporates µ-X-ray fluorescence (µ-XRF) and fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy to gain non-destructive insights into PFAS distribution in the impacted concrete. The μ-XRF and μ-XANES spectroscopy provided additional details on the detection of PFAS, which were not detected by the desorption electrospray ionization (DESI) imaging method conducted previously. The shorter chain PFAS were found on the top part of the concrete core (0.5 cm), and longer chain PFAS were mostly at the bottom part of the concrete core (5 cm). The inorganic fluorine fraction was also detected, and it likely hampered the detection of organic fluorine such as PFAS in the concrete. Thus, this non-destructive technique is an complementary approach to detect PFAS in contaminated concrete.

Sensitivity of mass flux reduction and mass removal of perfluoroalkyl substances to groundwater flow and transport parameter variability and heterogeneity

Heterogeneity of soil hydraulic (e.g., hydraulic conductivity (KS), porosity (θS)) and chemical (e.g., solid-phase adsorption (Kd)) properties complicates contaminant transport by creating spatial variability in sources of contaminant leaching. There is a knowledge gap on the effect of the interplay between these properties on the retardation and transport of per- and polyfluoroalkyl substances (PFAS) with different properties including carbon–fluorine chain-length and functional groups even in water-saturated conditions. Breakthrough curves have been used to evaluate PFAS transport behavior through heterogeneous media, including arrival time, maximum concentration, and tailing behavior. Contaminant mass flux reduction and mass removal correlations are also compared using numerical modeling to characterize PFAS transport through different source zones within a two-domain, heterogeneous system with comparison to homogeneous scenarios under water-saturated conditions. With heterogeneous properties, model sensitivity to KS was the highest among the other parameters and was controlled by the KS ratio between the different soils. The PFAS models in the homogeneous and heterogeneous scenarios were both sensitive to θS, depending on PFAS chain length. However, long-chain PFAS were less sensitive to θS variability compared to short-chain PFAS due to their higher Kd. The homogeneous and heterogeneous scenarios were equally sensitive to Kd variability, which was dependent on PFAS chain length.

Incorporating ultrashort-chain compounds into the comprehensive analysis of per- and polyfluorinated substances in potable and non-potable waters by LC-MS/MS

Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are small and very polar compounds with carbon chain lengths shorter than C4. Their ubiquitous and high levels of occurrence in environmental aquatic systems are emerging as a significant concern, rivaling the well-established issues associated with long-chain PFAS contamination. Therefore, it is important to analyze both USC and long-chain PFAS together in water samples to comprehensively assess and address the full spectrum of PFAS contamination. The high polarity of USC PFAS poses a challenge for standard chromatographic practices in PFAS analysis, primarily due to insufficient chromatographic retention. In this study, a simple and reliable workflow was developed for the simultaneous analysis of C1 to C14 perfluoroalkyl carboxylic and sulfonic acids, along with other groups of PFAS, in both potable and non-potable waters. The chromatographic separation was conducted using a polar-embedded reversed-phase LC column with an inert coating on the hardware. Three different water matrices (tap water, bottled water, sewage treatment wastewater) were chosen for method evaluation to demonstrate the applicability of the developed workflow for measuring 45 PFAS compounds in diverse water samples. A dilute-and-shoot workflow was evaluated by accuracy and precision analysis at five fortification levels, ranging from 2 to 250 ng/L. Eighteen isotopically labeled PFAS, serving as extracted internal standards, were added to the samples at 100 ng/L to validate the accuracy of the entire workflow. Calibration standards were prepared in reverse osmosis water due to its cleanliness for all analytes. The calibration ranges varied among different analytes, spanning from 1 – 1000 ng/L. All analytes and extracted internal standards exhibited recovery values ranging from 70% to 130% of the nominal concentration across all fortification levels. Satisfactory method precision was demonstrated with %RSD values below 20%. Additional potable and non-potable waters collected from various source waters were tested to further demonstrate that the established workflow is suitable for the accurate quantification of targeted PFAS in a wide range of water matrices.

Rapid Single-Step Detection of Polyfluoroalkyl Substances (PFAS) Using Electropolymerized Phenoxazine Dyes.

Per- and polyfluoroalkyl substances (PFAS) are highly stable ubiquitous contaminants that have been recently added to the list of regulated chemicals. While methods for PFAS detection exist, analysis is difficult, involving a tedious protocol and expensive instrumentation. Here, we demonstrate the first implementation of a phenoxazine dye as a sensing probe that facilitates rapid and inexpensive detection of representative PFAS, e.g., perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), at sensitivity levels covering the recently established Environmental Protection Agency (EPA) limits. The method comprises an electrode modified with a stable redox film of Meldola blue (MB) in its electropolymerized form (epMB), which provides amino sites for electrostatic interactions with PFAS. Long-chain PFAS bind specifically to the epMB, inducing a hydrophobic-type cluster formation through ion-pair and F-F interactions. This binding generates concentration-dependent changes in the epMB/epMB+ oxidation, enabling rapid and sensitive quantification in a single step with high sensitivity, reaching a limit of detection of 0.4 ppt for PFOS and 1.65 ppt for PFOA. The sensor demonstrates good selectivity toward common interfering compounds like humic acid, sodium chloride and fluoride, metallic ions (Cu, Hg, As), as well as pesticides. In addition to PFOS and PFOA, the sensors can measure other perfluoroalkyl compounds, demonstrating potential as a tool for rapid quantification of a total PFAS index, with affinity for long-chain PFAS. This work highlights the integration of redox receptors into an electrochemical sensor to solve the grand challenge of PFAS analysis using a rapid and inexpensive procedure, with potential for field deployment.

Unraveling the long-term gastrointestinal impact of perinatal perfluorobutane sulfonate exposure on rat offspring: Intestinal barrier dysfunction and Th17/Treg imbalance

Per- and polyfluoroalkyl substances (PFAS), especially long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), are increasingly acknowledged as a potential inflammatory bowel diseases (IBD) risk factor. Perfluorobutane sulfonate (PFBS), one kind of shorter chain alternative, has been reported to exhibit similar health hazards to those long-chain PFAS. However, the underlying mechanism underpinning PFBS-induced colonic inflammation has not been sufficiently elucidated. The T-helper-17 (Th17)/regulatory T (Treg) imbalance is a crucial event for the pathogenesis of colonic inflammation. In this study, we aimed to reveal whether and how perinatal PFBS exposure leads to the Th17/Treg imbalance and colonic inflammation in offspring. We firstly demonstrated in vivo that early-life PFBS exposure (0.5 mg/kg, 5 mg/kg) led to increased intestinal permeability and colonic inflammation accompanied by decreased expressions of tight junction protein 1 (Tjp1) and claudin-4 (Cldn4) and increased expressions of interleukin 17A (IL-17A) in colon of rat offspring. Further results indicated that PFBS exposure induces the Th17/Treg imbalance through upregulating the expression of retinoic acid receptor-related orphan receptor gamma t (Ror-γt) and transforming growth factor beta (TGF-β) and downregulating of forkhead box protein 3 (Foxp3) and IL-10 in colon. Moreover, metabolomics analyses indicated that bile secretion metabolism was significantly altered under PFBS exposure. The reduction of lithocholic acid and deoxycholic acid was closely related to the changes of TGF-β and IL-10 in colon, and may contribute to the perturbation of Th17/Treg balance and colonic inflammation. These results provide evidences for the immunotoxicity of PFBS and reveal the potential contribution to colonic inflammation, which raises concern on the health effects and risk assessment of short-chain PFAS.

Sorption of per- and polyfluoroalkyl substances by lignin in pulp and paper wastewater

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals commonly found in the environment. PFAS pose multifaceted challenges including identifying sources and exposure pathways, detecting and quantifying their presence, characterizing their fate and transport, and assessing their risks. PFAS and fluorotelomer polymers can be found in the pulp and paper (P&P) wastewater systems, but their behavior remains poorly understood. The constituents of P&P waste include lignin hydrolysis products, hence PFAS interactions with lignin likely affect PFAS removal efforts. This study employed quantitative ultra-performance liquid chromatography triple quadrupole mass spectrometry (UPLC-MS/MS) to investigate the sorption-desorption capacity and mechanisms of PFAS interaction with lignin. PFAS with sulfonate functional groups displayed higher affinity for lignin (solid phase) based on their partitioning coefficient (Kd), while PFAS with carboxylate head groups persisted in the P&P wastewater (aqueous phase). Sorption to lignin exhibited an increase with chain length (CF2)n among compounds with the same functional group. Long-chain (C ≥ 6) PFAS demonstrated higher sorption compared to short-chain (C ≤ 5) homologs. The sorption-desorption capacities, partitioning coefficients, and kinetics of PFAS reported in this study can facilitate predictive models for PFAS and assist in the development of efficient P&P waste treatment and management.

Adverse Outcomes Following Exposure to Perfluorooctanesulfonamide (PFOSA) in Larval Zebrafish (Danio rerio): A Neurotoxic and Behavioral Perspective.

Toxicity mechanisms of per- and polyfluoroalkyl substances (PFASs), a chemical class present in diverse ecosystems, as well as many of their precursors, have been increasingly characterized in aquatic species. Perfluorooctanesulfonamide (PFOSA, C8H2F17NO2S) is a common precursor of perfluorooctane sulfonic acid (PFOS), a long-chain PFAS. Here, we assessed sub-lethal endpoints related to development, oxidative stress, transcript levels, and distance moved in zebrafish embryos and larvae following continuous exposure to PFOSA beginning at 6 h post-fertilization (hpf). PFOSA decreased survival in fish treated with 1 µg/L PFOSA; however, the effect was modest relative to the controls (difference of 10%). Exposure up to 10 µg/L PFOSA did not affect hatch rate, nor did it induce ROS in 7-day-old larvae fish. The activity of larval fish treated with 100 µg/L PFOSA was reduced relative to the solvent control. Transcripts related to oxidative stress response and apoptosis were measured and BCL2-associated X, apoptosis regulator (bax), cytochrome c, somatic (cycs), catalase (cat), superoxide dismutase 2 (sod2) were induced with high concentrations of PFOSA. Genes related to neurotoxicity were also measured and transcript levels of acetylcholinesterase (ache), elav-like RNA binding protein 3 (elavl3), growth-associated protein 43 (gap43), synapsin II (syn2a), and tubulin 3 (tubb3) were all increased in larval fish with higher PFOSA exposure. These data improve our understanding of the potential sub-lethal toxicity of PFOSA in fish species.

From wastewater to feed: Understanding per- and polyfluoroalkyl substances occurrence in wastewater-irrigated crops.

Reusing treated wastewater for irrigation is a sustainable way to recycle nutrients and reduce freshwater use. However, wastewater irrigation inadvertently introduces per- and polyfluoroalkyl substances (PFAS) into agroecosystems, causing concerns regarding potential adverse effects to ecosystem, animal, and human health. Therefore, a better understanding of the pathways by which PFAS accumulate in forage crops is needed. A greenhouse study was conducted to (1) quantify the contribution of root uptake versus foliar sorption of PFAS in corn (Zea mays) and orchard grass (Dactylis glomerata), (2) assess effects of PFAS-impacted wastewater irrigation on plant health, and (3) determine the potential implications for bioaccumulation. The greenhouse study was composed of four treatments for each forage crop to isolate the relative contribution of two uptake pathways. Results suggested that foliar sorption was an unlikely contributor to PFAS concentrations observed in crop tissue. Root uptake was identified as the predominant uptake pathway. PFAS were detected more frequently in orchard grass samples compared to corn silage samples. Additionally, corn exhibited a lower uptake of long-chain PFAS compared to grass. Overall, no plant health effects on growth attributable to PFAS concentrations were observed.Forage data suggest cattle exposure to PFAS would be largely short-chain PFAS or long-chain "replacement" compounds(>50%). However, cattle may still be exposed to potentially harmful long-chain PFAS; levels in the forage crops exceeded the tolerable weekly intake set by the European Food Safety Authority. This study provides insights on PFAS entry into the food chain and potential implications for livestock and human health.

Integrating redox-electrodialysis and electrosorption for the removal of ultra-short- to long-chain PFAS

A major challenge in per- and polyfluoroalkyl substances (PFAS) remediation has been their structural and chemical diversity, ranging from ultra-short to long-chain compounds, which amplifies the operational complexity of water treatment and purification. Here, we present an electrochemical strategy to remove PFAS from ultra-short to long-chain PFAS within a single process. A redox-polymer electrodialysis (redox-polymer ED) system leverages a water-soluble redox polymer with inexpensive nanofiltration membranes, facilitating the treatment of varied chain lengths of PFAS without membrane fouling. Our approach combines both ion migration by electrodialysis (for PFAS with chain lengths ≤C4) and electrosorption strategies (for PFAS with chain lengths ≥C6) to eliminate approximately 90% of ultra-short-, short-chain, and long-chain PFAS. At the same time, we achieve continuous desalination of the source water down to potable water level. The redox-polymer ED exhibits remarkable PFAS removal in real source water scenarios, including from matrices with 10,000 times higher salt concentrations, as well as secondary effluents from wastewaters. Additionally, the removed PFAS is mineralized with a defluorination performance between 76-100% by electrochemical oxidation, highlighting the viability of integrating the separation step with a reactive degradation process.

Fate of per- and polyfluoroalkyl substances at a 40-year dedicated municipal biosolids land disposal site

The fate of per- and polyfluoroalkyl substances (PFAS) was evaluated at a site where municipal biosolids have been applied annually for 38 years as a waste management strategy. Soil cores (1.8 m in 30-cm sections), groundwater from four wells, and biosolids applied in 2022 were analyzed for PFAS (54 targeted, 17 semi-quantified) using liquid chromatography high resolution mass spectrometry including suspect screening. Total PFAS concentrations decreased with soil depth from 1700 ng/g to 2.06 ng/g. PFAS distribution in 2022 biosolids were 60 mol% perfluoroalkyl acid (PFAA) precursors and intermediates. The surface soil was dominated by long-chain PFAAs (67–76 mol%) reflecting precursor degradation after biosolids application. Presence of semi-quantified intermediates further reflects precursor degradation in surface soil. Long-chain PFAAs diminished with depth while short-chain PFAAs increased with up to 98 and 96 mol% short-chain PFAAs in the bottom depth and groundwater, respectively. PFAS distribution with depth is consistent with chain-length dependent sorption-impacted transport and the high organic carbon content of the surface soil (15.2 % OC) which subsequently decreased with depth (~2–3 % OC at >60 cm). High organic carbon content in the upper horizon is likely from decades of high biosolids application rates, which contributed to minimizing leaching of long-chain PFAS. While the well within the dedicated land disposal is not drinking water, for comparison only, PFAS concentrations in this well only marginally exceeded the EU drinking water directive for total PFAS and a few individual short-chain PFAS, but did exceed tenfold, the USEPA drinking water standard for PFOA.

Per- and Polyfluoroalkyl (PFAS) Disruption of Thyroid Hormone Synthesis.

Per- and polyfluoroalkyl substances (PFAS) are a group of environmental pollutants that have been linked to a variety of health problems in humans, including the disruption of thyroid functions. Herein, for the first time, the impact of PFAS on thyroid hormone synthesis is shown. Mid- to long-chain PFAS impact thyroid hormone synthesis by changing the local hydrogen bond network as well as the required orientation of hormonogenic residues, stopping the production of thyroxine (T4). Furthermore, the toxic effects of sulfonic PFAS are more prominent than those of carboxylic PFAS, highlighting that the exposure to these specific compounds can pose greater problems for thyroid homeostasis.

Causative mechanisms limiting the removal efficiency of short-chain per- and polyfluoroalkyl substances (PFAS) by activated carbon

Short-chain per and polyfluoroalkyl substances (PFAS) have been found to be relatively high in water treatment systems compared to long-chain PFAS because of the unsatisfactory adsorption efficiency of short-chain PFAS. Knowledge about why short-chain PFAS are less removed by porous carbon is very limited. The study focused on providing causal mechanisms that link the low adsorption of short-chain PFAS and proposing an improved method for removing both short- and long-chain PFAS. The long-chain PFAS with higher hydrophobicity diffused more quickly than the short-chain PFAS due to stronger partitioning driving forces. In the initial adsorption stage, therefore, pores of activated carbon were blocked by long-chain PFAS, which makes it difficult for the short-chain PFAS to enter the internal pores. Although several short-chain PFAS diffuse into the pores, the relatively more hydrophilic short-chain congeners cannot be fully adsorbed on activated carbon due to limited positively charged sites. Moreover, compared to larger particle sizes, smaller activated carbon particles have shorter pore channels near the surface, reducing the risk of pore-blocking and ensuring the pores remain accessible for more efficient adsorption. Additionally, these smaller particles offer a greater external surface area and more functional groups, which enhance the adsorption capacity. It indicates that the smaller particle size of activated carbon would have a positive effect on the short-chain PFAS removal.