Short-chain Perfluoroalkyl Substances Research Articles

Efficient removal of perfluorobutanesulfonic acid from water through a chitosan/polyethyleneimine xerogel

Due to the recently ratified legislations, the use of long-chain poly- and perfluoroalkyl substances (PFASs) must be reduced and in the absence of a safe alternative, short-chain PFASs are currently used in their place. The continuously growing utilization of the short-chain PFASs, results in their abrupt introduction in the environment, and highlights the importance of adopting efficient remediation strategies. This study addresses an appropriate solution to remove perfluorobutanesulfonic acid (PFBS) from aqueous media through a static adsorption process. Specifically, a chitosan/polyethyleneimine based composite xerogel was prepared and its ability to remove PFBS from water was studied in detail. Behavioral patterns of the PFBS adsorption process were perused over a broad range of concentrations from ppb to ppm, and the adsorption studies reveal that the maximum PFBS adsorption capacity reaches up to 305 mg/g within 24 h from the beginning of the process. In addition to the electrostatic interaction between the amine groups of the xerogels and the negatively charged PFBS molecules, the formation of hydrogen bonds were also revealed by the chemical characterization and confirmed by molecular dynamics simulation studies.

Study on Pollution Characteristics of Perfluoroalkyl Substances (PFASs) in Shallow Groundwater

Perfluoroalkyl substances (PFASs) in shallow groundwater are increasingly being studied due to the global occurrence, environment persistence, bioaccumulation, and potential human health risk. In this research, 16 PFAS (11 perfluorinated carboxylic acids and 5 perfluorinated sulfonic acids) concentrations in groundwater were quantified to obtain information on geographical distribution and PFAS detection pattern for 4 years in South Korea. In the results, groundwater PFAS concentration ranged from non-detectable to average 45.2 ng/L (sum of PFASs). The major PFAS compounds were perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS). The short chain (C < 8) PFASs were more prevalent than long chain (C > 8) PFASs in shallow groundwater. However, the detection patterns of 15 PFASs were different for each aquifer. Subsequently, through a health risk assessment, a non-carcinogenic risk level through ingestion, inhalation, and dermal contact for PFOA and PFOS was determined at 10−1, and it presents the need for PFAS management of groundwater.

Imparting Selective Fluorophilic Interactions in Redox Copolymers for the Electrochemically Mediated Capture of Short-Chain Perfluoroalkyl Substances

With increasing regulations on per- and polyfluoroalkyl substances (PFAS) across the world, understanding the molecular level interactions that drive their binding by functional adsorbent materials is key to effective PFAS removal from water streams. With the phaseout of legacy long-chain PFAS, the emergence of short-chain PFAS has posed a significant challenge for material design due to their higher mobility and hydrophilicity and inefficient removal by conventional treatment methods. Here, we demonstrate how cooperative molecular interactions are essential to target short-chain PFAS (from C4 to C7) by tailoring structural units to enhance affinity while modulating the electrochemical control of capture and release of PFAS. We report a new class of fluorinated redox-active amine-functionalized copolymers to leverage both fluorophilic and electrostatic interactions for short-chain PFAS binding. We combine molecular dynamics (MD) simulations and electrosorption to elucidate the role of the designer functional groups in enabling affinity toward short-chain PFAS. Preferential interaction coefficients from MD simulations correlated closely with experimental trends: fluorination enhanced the overall PFAS uptake and promoted the capture of less hydrophobic short-chain PFAS (C ≤ 5), while electrostatic interactions provided by secondary amine groups were sufficient to capture PFAS with higher hydrophobicity (C ≥ 6). The addition of an induced electric field showed favorable kinetic enhancement for the shortest PFAS and increased the reversibility of release from the electrode. Integration of these copolymers with electrochemical separations showed potential for removing these contaminants at environmentally relevant conditions while eliminating the need for chemical regeneration.

Sorptive removal of short-chain perfluoroalkyl substances (PFAS) during drinking water treatment using activated carbon and anion exchanger

Laboratory tests and column tests were carried out in a waterwoks to investigate the removal of short- and long-chain PFAS using activated carbon filtration and ion exchange treatment. For all adsorbents, the sorption affinity of short-chain per- and polyfluoroalkyl carboxylic acids (PFCA) was significantly lower than that of long-chain PFAS or short-chain per- and polyfluoroalkyl sulfonic acids (PFSA). In the PFAS-polluted groundwater matrix, the short-chain PFCA PFBA and PFPeA could only be sufficiently removed with activated carbon over short run times of 6000 and 11,000 bed volumes (BV), respectively. Longer PFCA with a chain length of C6 or more were removed over longer run times.The removal of short-chain PFCA using ion exchange media could also only be achieved over relatively short run times of 5000 BV for PFBA, 10,000BV for PFPeA and 18,000 BV for PFHxA. These are sometimes significantly longer than those of activated carbon. Due to the higher material costs for ion exchange media, there are nevertheless no lower operating costs when the ion exchangers are used in single-use mode. However, ion exchangers can be regenerated and then reused which can result in economic advantages compared to activated carbon filtration. However, for the extensive regeneration, especially for the elution of the long-chain PFAS, the additional use of ethanol is needed in the process. In contrast, the short-chain PFBA and PFPeA can be extracted without organic solvent from a weakly basic ion exchanger.

Different Sources, Fractionation, and Migration of Legacy and Novel Per- and Polyfluoroalkyl Substances between Greenhouse and Open-Field Soils.

Perfluoroalkyl substances (PFASs) are widely present in agricultural soils, but their sources and fate in greenhouse soils remain unclear. In this study, the sources, fractionation, and migration of PFASs were compared in the greenhouse and open-field soils of the Fen-Wei Plain, China. The total concentrations of PFASs (Σ17PFAS) were comparable in the greenhouse and open-field soils but with different profiles. Detrended correspondence and correlation analyses indicated that dry deposition was an important source of PFASs in the open-field soils, whereas surface water had a notable contribution to the greenhouse soils due to more frequent irrigation. The PFASs in the soils were mainly present in water-soluble fraction (F1). The F1 proportions of short-chain and long-chain PFASs were negatively correlated with the anion exchange capacity (AEC) and organic carbon content (foc) in soil, respectively, with that of short-chain PFASs being higher than long-chain ones. The AEC was significantly higher while foc was lower in the greenhouse soil than the open-field soil, leading to lower proportions of F1 for short-chain PFASs while higher for long-chain ones in the greenhouse soil. Frequent irrigation and elevated temperatures promoted the migration of PFASs in greenhouse soil; thus, the Σ17PFAS and F1 exhibited an increasing trend with soil depth.

Insights into the Dermal Absorption, Deposition, and Elimination of Poly- and Perfluoroalkyl Substances in Rats: The Importance of Skin Exposure.

Humans are frequently exposed to poly- and perfluoroalkyl substances (PFASs) via direct skin contact with personal care and consumer products containing them. Here, we used a rat model to estimate the dermal penetration efficiency of 15 representative PFASs. After 144 h post-dosing, 4.1-18.0 and 5.3-15.1% of the applied PFASs in the low (L) and high (H) groups, respectively, were absorbed into the rats. PFAS absorption and permeation were parabolically associated with the perfluorinated carbon chain length (CF), peaking for perfluoroheptanoic acid (PFHpA). The lipid-rich stratum corneum of the skin barrier substantially suppressed the penetration of less hydrophobic short-chain PFASs, whereas the water-rich viable epidermis and dermis served as obstacles to hydrophobic long-chain PFAS permeation. However, the renal clearance (CLrenal) of the target PFAS decreased with increasing CF, suggesting that urinary excretion is crucial to eliminate less hydrophobic short-chain PFASs. Notably, the peak times of PFASs in the systemic circulation of rats (8-72 h) were remarkably longer than those after oral administration (1-24 h). These results suggest that dermal penetration can be long-lasting and contribute considerably to the body burden of PFASs, especially for those with moderate hydrophobicity due to their favorable skin permeation and unfavorable urinary excretion.

XGBoost model as an efficient machine learning approach for PFAS removal: Effects of material characteristics and operation conditions

Due to the implications of poly- and perfluoroalkyl substances (PFAS) on the environment and public health, great attention has been recently made to finding innovative materials and methods for PFAS removal. In this work, PFAS is considered universal contamination which can be found in many wastewater streams. Conventional materials and processes used to remove and degrade PFAS do not have enough competence to address the issue particularly when it comes to eliminating short-chain PFAS. This is mainly due to the large number of complex parameters that are involved in both material and process designs. Here, we took the advantage of artificial intelligence to introduce a model (XGBoost) in which material and process factors are considered simultaneously. This research applies a machine learning approach using data collected from reported articles to predict the PFAS removal factors. The XGBoost modeling provided accurate adsorption capacity, equilibrium, and removal estimates with the ability to predict the adsorption mechanisms. The performance comparison of adsorbents and the role of AI in one dominant are studied and reviewed for the first time, even though many studies have been carried out to develop PFAS removal through various adsorption methods such as ion exchange, nanofiltration, and activated carbon (AC). The model showed that pH is the most effective parameter to predict PFAS removal. The proposed model in this work can be extended for other micropollutants and can be used as a basic framework for future adsorbent design and process optimization.

Perfluorobutanoic Acid (PFBA) Induces a Non-Enzymatic Oxidative Stress Response in Soybean (Glycine max L. Merr.).

Short-chain perfluoroalkyl substances (PFAS) are generally considered to be of less environmental concern than long-chain analogues due to their comparatively shorter half-lives in biological systems. Perfluorobutanoic acid (PFBA) is a short-chain PFAS with the most root–shoot transfer factor of all PFAS. We investigated the impact of extended exposure of soybean plants to irrigation water containing environmentally relevant (100 pg–100 ng/L) to high (100 µg–1 mg/L) concentrations of PFBA using phenotypical observation, biochemical characterization, and transcriptomic analysis. The results showed a non-monotonous developmental response from the plants, with maximum stimulation and inhibition at 100 ng/L and 1 mg/L, respectively. Higher reactive oxygen species and low levels of superoxide dismutase (SOD) and catalase (CAT) activity were observed in all treatment groups. However transcriptomic analysis did not demonstrate differential expression of SOD and CAT coding genes, whereas non-enzymatic response genes and pathways were enriched in both groups (100 ng/L and 1 mg/L) with glycine betaine dehydrogenase showing the highest expression. About 18% of similarly downregulated genes in both groups are involved in the ethylene signaling pathway. The circadian rhythm pathway was the only differentially regulated pathway between both groups. We conclude that, similar to long chain PFAS, PFBA induced stress in soybean plants and that the observed hormetic stimulation at 100 ng/L represents an overcompensation response, via the circadian rhythm pathway, to the induced stress.

Environmental specimen banks and the European Green Deal

The study highlights the potential of Environmental Specimen Banks (ESBs) for implementing the Zero Pollution Ambition and the Biodiversity Strategy of the European Green Deal. By drawing on recent monitoring studies of European ESBs, we illustrate the role ESBs already play in assessing the state of ecosystems in Europe and how they help to make developments over time visible. The studies reveal the ubiquitous presence of per- and polyfluoroalkyl substances, halogenated flame retardants, chlorinated paraffins, plasticizers, cyclic volatile methyl siloxanes, UV-filters, pharmaceuticals, and microplastics in the European environment. Temporal trends demonstrate the effectiveness of European regulations on perfluorooctane sulfonic acid, pentabrominated diphenylethers and diethylhexyl phthalate, but also point to the rise of substitutes such as non-phthalate plasticizers and short-chain perfluoroalkyl substances. Other studies are wake-up calls indicating the emergence of currently unregulated compounds such as long-chain chlorinated paraffins. Ecological studies show temporal trends in biometric parameters and stable isotope signatures that suggest long-term changes in environmental conditions. Studies on biodiversity of ecosystems using environmental DNA are still in their beginnings, but here too there is evidence of shifts in community composition that can be linked to changing environmental conditions. This review demonstrates the value of ESBs (a) for describing the status of the environment, (b) for monitoring temporal changes in environmental pollution and the ecologic condition of ecosystems and thereby (c) for supporting regulators in prioritizing their actions towards the objectives of the Green Deal.

Simultaneous removal of multiple PFAS from contaminated groundwater around a fluorochemical facility by the periodically reversing electrocoagulation technique

Increasing attentions have been paid on widespread contaminations of perfluoroalkyl substances (PFAS). Particularly, simultaneous occurrence of multiple PFAS in the aquatic environments globally has been recognized as a crucial emerging issue. The present study aimed to perform simultaneous removal of multiple PFAS contaminations from groundwater around a fluorochemical facility based upon the technique of periodically reversing electrocoagulation (PREC). Accordingly, the experiments were implemented on the best conditions, actual application, and removal mechanism in the process of PREC with Al–Zn electrodes. Consequently, 1 mg/L synthetic solution of ten PFAS could be eliminated ideally during the initial 10 min, under the optimal conditions involving voltage at 12 V, pH at 7.0, and electrolyte with NaCl. The maximum removal rates of perfluorobutanoic acid (PFBA), perfluorobutane sulfonate (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonate (PFOS) were 90.9%, 91.0%, 99.7%, and 100%, respectively. The PREC performed a significant improvement for the wide scope of PFAS removal with the levels ranging from 10 μg/L to 100 mg/L. In addition, the optimized PREC technique was further applied to remove various PFAS contaminations from the natural groundwater samples underneath the fluorochemical facility, subsequently generating the removal efficiencies in the range between 31.3% and 99.9%, showing the observable advantages compared with other removal techniques for the actual application. Finally, the mechanism of PFAS removal was mainly related to enmeshment and synergistic bridging adsorption, together with oxidation degradation that determined by potential formation of short-chain PFAS in the PREC process. As a result, the PREC technique would be a promising technique for the efficient removal of multiple PFAS contaminations simultaneously from natural water bodies.

Adsorption, Structure, and Dynamics of Short- and Long-Chain PFAS Molecules in Kaolinite: Molecular-Level Insights.

The ubiquitous presence of poly- and perfluoroalkyl substances (PFAS) in different natural settings poses a serious threat to environmental and human health. Soils and sediments represent one of the important exposure pathways of PFAS for humans and animals. With increasing bioaccumulation and mobility, it is extremely important to understand the interactions of PFAS molecules with the dominant constituents of soils such as clay minerals. This study reports for the first time the fundamental molecular-level insights into the adsorption, interfacial structure, and dynamics of short- and long-chain PFAS molecules at the water-saturated mesopores of kaolinite clay using classical molecular dynamics (MD) simulations. At environmental conditions, all the PFAS molecules are exclusively adsorbed near the hydroxyl surface of the kaolinite, irrespective of the terminal functional groups and metal cations. The interfacial adsorption structures and coordination environments of PFAS are strongly dependent on the nature of the functional groups and their hydrophobic chain length. The formation of large, aggregated clusters of long-chain PFAS at the hydroxyl surface of kaolinite is responsible for their restricted dynamics in comparison to short-chain PFAS molecules. Such comprehensive knowledge of PFAS at the clay mineral interface is critical to developing novel site-specific degradation and mitigation strategies.

How perfluoroalkyl substances modify fluorinated self-assembled monolayer architectures: An electrochemical and computational study

There is an urgent need for sensing strategies to screen perfluoroalkyl substances (PFAS) in aqueous matrices. These strategies must be applicable in large-scale monitoring plans to face the ubiquitous use of PFAS, their wide global spread, and their fast evolution towards short-chain, branched molecules. To this aim, the changes in fluorinated self-assembled monolayers (SAM) with different architectures (pinholes/defects-free and with randomized pinholes/defects) were studied upon exposure to both long and short-chain PFAS. The applicability of fluorinated SAM in PFAS sensing was evaluated. Changes in the SAM structures were characterised combining electrochemical impedance spectroscopy and voltammetric techniques. The experimental data interpretation was supported by molecular dynamics simulations to gain a more in-depth understanding of the interaction mechanisms involved. Pinhole/defect-free fluorinated SAM were found to be applicable to long-chain PFAS screening within switch-on sensing strategy, while a switch-off sensing strategy was reported for screening of both short/long-chain PFAS. These strategies confirmed the possibility to play on fluorophilic interactions when designing PFAS screening methods.

Perfluoroalkyl substances in marine food webs from South China Sea: Trophic transfer and human exposure implication

Perfluoroalkyl substances (PFASs) are known to be persistent and toxic, and can be accumulated and trophic magnified in the environments. PFASs are widely distributed, and their coastal input poses a threat to the health of aquatic organisms and local residents. In present study, 17 PFASs including one emerging polyether substitute in water, sediment, and organisms were investigated from the South China Sea. Perfluorobutanoic acid (PFBA) was predominant in water, of which concentration ranged from ND to 10.26 ng/L, with a mean of 5.21 ng/L. Similar to sediment and organisms, PFBA was the substance with the highest concentration detected among PFASs. This result seemingly indicated that use of short-chain PFASs as substitutes for long-chain PFASs in recent years. Trophic magnification factors (TMFs) of PFASs were estimated in the marine food web. TMFs > 1 was observed only in perfluorooctane sulfonic acid (PFOS), indicating a biomagnification potential of PFOS in the given ecosystem. The estimated daily intake (EDI) of PFOS and PFOA were most prevalent in mollusk, whereas the EDI of PFBA was greater in fish and shrimp. The hazard ratio (HR) reported for seven dominant PFASs were lower than 1, which suggests that PFASs via seafood consumption would not cause significant health risk to local residents.

Early Warnings by Liver Organoids on Short- and Long-Chain PFAS Toxicity.

Short-chain per-fluoroalkyl substances (PFAS) have replaced long-chains in many applications, however the toxicity and its mode of action and interactions due to the large number of these compounds and their mixtures is still poorly understood. The paper aims to compare the effects on mouse liver organoids (target organ for bioaccumulation) of two long-chain PFAS (perfluorooctane sulfonate -PFOS-, perfluorooctanoic acid -PFOA) and two short-chain PFAS commonly utilized in the industry (heptafluorobutyric acid -HFBA-, Pentafluoropropionic anhydride-PFPA) to identify the mode of action of these classes of contaminants. Cytomorphological aberrations and ALT/GDH enzyme disruption were identified but no acute toxicity endpoint neither apoptosis was detected by the two tested short-chain PFAS. After cytomorphological analysis, it is evident that short-chain PFAS affected organoid morphology inducing a reduction of cytostructural complexity and aberrant cytological features. Conversely, EC50 values of 670 ± 30 µM and 895 ± 7 µM were measured for PFOS and PFOA, respectively, together with strong ALT/GDH enzyme disruption, caspase 3 and 7 apoptosis activation and deep loss of architectural complexity of organoids in the range of 500–1000 µM. Eventually, biochemical markers and histology analysis confirmed the sensitivity of organoid tests that could be used as a fast and reproducible platform to test many PFAS and mixtures saving time and at low cost in comparison with in vivo tests. Organoids testing could be introduced as an innovative platform to assess the toxicity to fast recognize potentially dangerous pollutants.

A Review of Treatment Techniques for Short-Chain Perfluoroalkyl Substances

In recent years, an increasing amount of short-chain perfluoroalkyl substance (PFAS) alternatives has been used in industrial and commercial products. However, short-chain PFASs remain persistent, potentially toxic, and extremely mobile, posing potential threats to human health because of their widespread pollution and accumulation in the water cycle. This study systematically summarized the removal effect, operation conditions, treating time, and removal mechanism of various low carbon treatment techniques for short-chain PFASs, involving adsorption, advanced oxidation, and other practices. By the comparison of applicability, pros, and cons, as well as bottlenecks and development trends, the most widely used and effective method was adsorption, which could eliminate short-chain PFASs with a broad range of concentrations and meet the low-carbon policy, although the adsorbent regeneration was undesirable. In addition, advanced oxidation techniques could degrade short-chain PFASs with low energy consumption but unsatisfied mineralization rates. Therefore, combined with the actual situation, it is urgent to enhance and upgrade the water treatment techniques to improve the treatment efficiency of short-chain PFASs, for providing a scientific basis for the effective treatment of PFASs pollution in water bodies globally.

Thermal decomposition of heptafluoropropylene-oxide-dimer acid (GenX)

Incineration appears as a viable strategy in the disposal of the notorious perfluoroalkyl substances (PFASs) in a process that typically leads to fluorine mineralization. Central in the design of such operation is to comprehend the underlying chemical mechanisms that dictate thermal fragmentation of PFASs into smaller perfluorinated cuts and HF. Among notable short-chain PFASs entities is the heptafluoropropylene-oxide-dimer acid (HFPO-DA, C5F11C(O)OH), commercially known as GenX synthesized as a possible replacement of other PFASs compounds. However, reaction pathways that underpin the degradation of GenX at temperatures relevant to its decomposition in incinerators (i.e., cement kilns), remain unknown. Herein, we map out all plausible initial reactions that govern the thermal decomposition of GenX. Simultaneous elimination of HF and CO2 appears as the kinetically most favored channel with an accessible activation enthalpy of ∼62.0 kcal/mol. Fission of the ether linkage in the 1,1,1,2,2,3,3-heptafluoro-3-[(1-fluoroethenyl)oxy] propane molecule (that forms after HF/CO2 elimination) affords a wide array of CnFm cuts, most notably CF2 at elevated temperatures. Constructed kinetic model plots temperature-dependent profiles of important species. It is predicted that GenX to commence decomposition around 700 K at a residence time of 2.0 s, a value that is generally applied in incinerators. Findings from the study call to further investigate interactions between the predicted major fluorine carriers (HF and CF2) and other constituents encountered in relevant incineration mediums, most notably, calcium hydroxides and polymeric materials.

Using comprehensive lipid profiling to study effects of PFHxS during different stages of early zebrafish development

PFHxS (Perfluorohexane sulfonic acid) is one of the short-chain perfluoroalkyl substances (PFASs) which are widely used in many industrial and consumer applications. However, limited information is available on the molecular mechanism of PFHxS toxicity (e.g. lipid metabolism). This study provides in-depth information on the lipid regulation of zebrafish embryos with and without PFHxS exposure. Lipid changes throughout zebrafish development (4 to 120 h post fertilization (hpf)) were closely associated with lipid species and lipid composition (fatty acyl chains). A comprehensive lipid analysis of four different PFHxS exposures (0, 0.3, 1, 3, and 10 μM) at different zebrafish developmental stages (24, 48, 72, and 120 hpf) was performed. Data on exposure concentration, lipids, and developmental stage showed that all PFHxS concentrations dysregulated the lipid metabolism and these were developmental-dependent. The pattern of significantly changed lipids revealed that PFHxS caused effects related to oxidative stress, inflammation, and impaired fatty acid β-oxidation. Oxidative stress and inflammation caused the remodeling of glycerophospholipid (phosphatidylcholine (PC) and phosphatidylethanolamine (PE)), with increased incorporation of omega-3 PUFA and a decreased incorporation of omega-6 PUFA.

Abstract 12258: Associations Between Serum Perfluoroalkyl Substances and Vascular Function

Introduction: Perfluoroalkyl substances (PFA)s are ubiquitous synthetic organic compounds used in packaging, flame retardants and stain resistant fabric. The use of older, long-chain, persistent PFAs in the U.S. has been phased out due to cardiometabolic health effects and replaced with short-chain, less persistent, alternative PFAs for which little data on cardiotoxicity exists. We evaluated the relationships between serum PFAs and noninvasive measures of vascular function by carotid-femoral pulse wave velocity (PWV) and brachial artery reactivity testing (BART). Methods: We measured 14 serum PFAs using hybrid solid-phase extraction and ultrahigh-performance liquid chromatography-tandem mass spectrometry in 94 adult outpatients without CVD from an urban medical center. Using medical records and questionnaires, we collected demographic and clinical data; and measured PWV and BART using standard protocols. We assessed associations of individual PFAs with log-transformed BART and PWV using linear regression. We used weighted quantile sum regression to assess effects of correlated PFA mixtures on BART and PWV. Results: Of the 14 measured PFAs, 10 were detectable in >50% of samples, and were included for analysis. Each standard deviation increase in perfluroheptanoic acid (PFHpA) was associated with -0.17 (-0.34, -0.002) decrease in log BART. The weighted index of PFAs in mixture 1 (Table) was significantly and inversely associated with log BART; each tertile increase in the weighted index of mixture 1 was associated with a -0.29 (-0.52, -0.06) decrease in log BART, with PFHpA having the greatest weight (0.73) in the mixture. In contrast, neither individual PFAs nor PFA mixtures were associated with PWV. Conclusions: Increasing concentrations of a new, short-chain PFA, PFHpA, are associated with impaired vascular function among outpatients without CVD. Our findings contribute evidence of potential adverse cardiovascular effects of currently used PFAs.

Perfluoroalkyl substances in water, sediment, and fish from a subtropical river of China: Environmental behaviors and potential risk

Perfluoroalkyl substances (PFAS) in water, sediment and fish were analyzed from a subtropical river, Jiulong River in the southeast of China, to character the sources, seasonal variations, bioconcentration and potential risk. PFAS in water, sediment, muscle and liver tissues of fish ranged from 2.5 to 410 ng L−1, 0.24–1.9 ng g−1 dw, 25–100 and 35–1100 ng g−1 ww, respectively. Generally, perfluorohexanoic acid (PFHxA) was the dominant compound in water, while, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the dominant compounds in sediment and fish tissues. High concentrations of PFAS in water were found near the machinery manufacturing and paper packaging plants in the north branch of Jiulong River. PFAS during the dry season were significantly (P < 0.01) higher than that during the normal season and wet season. The Kd of PFAS increased with the carbon chain length, and perfluoroalkyl sulfonic acids (PFSAs) exhibited higher Kd values than perfluoroalkyl carboxylic acids (PFCAs), indicating these long chain PFAS tended to be adsorbed by sediment. Long chain PFAS exhibited high bioconcentration factors (BCFs), while short and medium carbon chain PFAS had weak bioconcentration capacity. The hazard ratios (HR) suggested that frequent consumption of river fish may pose health risks to local population.

Synergistic degradation of GenX (hexafluoropropylene oxide dimer acid) by pairing graphene-coated Ni-foam and boron doped diamond electrodes

Perfluoroalkyl substances (PFAS) are well-recognized water pollutants. Even though most studies have traditionally focused on long-chain PFAS, their progressive replacement by short-chain PFAS has made the latter a new motive of concern. For example, short-chain hexafluoropropylene oxide dimer acid (known as GenX) was introduced as a supposedly sustainable substitute for toxic perfluorooctanic acid, but is now being detected in several aquatic environments around the world, with various reports evidencing its harmful effects. In this work, we investigated the degradation/mineralization of GenX by electro-Fenton (EF) using a graphene-Ni-foam (Gr-Ni-foam) cathode paired with a boron doped diamond (BDD) anode. It was found that homogeneous •OH radicals formed by EF showed limited reactivity with the GenX molecule itself. Instead, GenX degradation was initiated by direct electron transfer at the BDD surface, and then homogeneous •OH continued and enhanced the degradation/mineralization process. In contrast, Pt and fluorine doped tin oxide (FTO) anodes did not favor GenX degradation. A synergy between EF and BDD oxidation achieved 92.2 ± 1.0% of GenX mineralization after 6 h of treatment at 16 mA cm−2, vs. only 9.2 ± 0.1% by EF alone and 73.6 ± 6.2% with BDD alone. Based on the degradation by-products detected by high performance liquid chromatography-mass spectrometry (HPLC-MS), a mineralization pathway for GenX is proposed, involving two different routes initiated by electron transfer at the carboxylic and ether groups of the GenX molecule.