Long-chain Perfluoroalkyl Substances Research Articles

Adsorption of perfluoroalkyl substances on deep eutectic solvent-based amorphous metal-organic framework: Structure and mechanism

Perfluoroalkyl substances (PFASs) are a class of emerging organic pollutants characterized by high toxicity, environmental persistence, and widespread detection in water sources. The removal of PFASs from water is a matter of global concern, given their detrimental impact on both the environment and public health. Many commonly used PFAS adsorbents demonstrate limited adsorption capacities and/or slow adsorption kinetics. Therefore, there is an urgent need for the development of efficient adsorbents. For the first time, this work systematically investigated the performance of a deep eutectic solvent (DES)-based amorphous metal-organic framework (MOF) for the adsorption of PFASs with different carbon-chain lengths under the state of the mixture in aquatic environments. The adsorption mechanism was probed by a suite of adsorption kinetics studies, adsorption isotherm profiling, spectral characterization, and ab initio molecular dynamics (AIMD) simulations, revealing that PFAS adsorption is driven by synergistic capturing effects including acid/base coordination, CF-π (carbon-fluorine-π), hydrogen bonding, and hydrophobic interactions. Furthermore, the adsorption processes of short-chain and long-chain targets were found to involve different rate-controlling steps and interaction sites. Hydrophobic interactions facilitated the swift arrival of long-chain PFASs at the coordinatively interacting sites between carboxyl termini and Lewis acid Zr unsaturated sites, thanks to their lower reaction barriers. On the other hand, the adsorption of short-chain PFASs primarily relied on a Zr hydroxyl-based ligand exchange force, which would take place at Brønsted acid sites. The existence of massive structural disorder in amorphous UiO-66 led to the development of larger pores, thus improving the accessibility of abundant adsorption sites and facilitating adsorption and diffusion. The presence of multiple types of interactions and flexible structure in defect-rich amorphous UiO-66 significantly increased the exposure of functional groups to the adsorbates. Additionally, this material possessed outstanding regeneration efficiency and outperformed other MOF-based adsorbents with high affinity for targets. It enhances our understanding of the adsorption performances and mechanisms of amorphous materials toward PFASs, thereby paving the way for designing more efficient PFAS adsorbents.

Insight into the differential toxicity of PFOA and PFBA based on a 3D-cultured MDA-MB-231 cell model

Perfluoroalkyl substances (PFASs) are a category of high-concerned emerging contaminants which are suspected to correlate with various human adverse health outcomes including tumors. It is also a question whether short-chain PFASs are qualified alternatives under the regulation of long-chain PFASs. In this study, a three-dimensional (3D) culture system based on Gelatin methacrylate (GelMA) hydrogel matrix was used to investigate the impacts of 120-h perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA) exposure of MDA-MB-231 cells. The results showed that PFOA exposure promoted the proliferation, migration, and invasion of MDA-MB-231 cells in an environmentally relevant concentration range (0.1 to 10 μM), exhibiting a clear malignant-promoting risk. In contrast, PFBA only showed a trend to induce non-invasive cell migration. Hippo/YAP signaling pathway was identified as the contributor to the differences between the two PFASs. PFOA but PFBA reduced YAP phosphorylation and increased the nuclear content of YAP, which further facilitated abundant key factors of epithelial-mesenchymal transition (EMT) process. Our results provided a new idea for the carcinogenicity of PFOA using a 3D-based paradigm. Although the effects by PFBA were much milder than PFOA in the current test duration, the cell model suitable for longer exposure is still necessary to better assess the safety of alternative short-chain PFASs.

Bioaccumulation Characteristics of Typical Perfluoroalkyl Compounds in Alfalfa Under Salt Stress.

Medicago sativa, commonly known as alfalfa, is widely distributed worldwide, known for its strong stress resistance and well-developed root system, making it an important plant in ecological restoration research. To investigate the absorption and transport characteristics of alfalfa for typical perfluoroalkyl substances (PFAS) under salt stress, a 30-day indoor greenhouse experiment was conducted. The results showed that alfalfa exhibited varying degrees of absorption and transport for the selected PFAS. The highest BCF (Bioconcentration Factor) for shoot tissue reached 725.4 (for PFBA), and the highest TF (Translocation Factor) reached 53.8 (for PFPeA). Different PFAS compounds exhibited distinct bioaccumulation behaviors, with short-chain PFAS more readily entering the plant's root system and being transported upwards, while long-chain PFAS tended to adsorb to the surface of the root system. Furthermore, salt stress did not significantly affect the uptake of PFAS by alfalfa. This suggests that alfalfa is salt-tolerant and holds great potential for ecological restoration in short-chain PFAS-contaminated sites.

Spatial distribution, isomer signature and air-soil exchange of legacy and emerging poly- and perfluoroalkyl substances

Widespread occurrences of various poly- and perfluoroalkyl substances (PFAS) in terrestrial environment calls for the growing interest in their transport behaviors. However, limited studies detected PFAS with structural diversity in tree barks, which reflect the long-term contamination in atmosphere and play a vital role in air-soil exchange behaviors. In this study, 26 PFAS congeners and typical branched isomers were investigated in surface soils and tree barks at 28 sites along the Taihu Lake, Taipu River, and Huangpu River. Concentrations of total PFAS in soils and tree barks were 0.991–29.4 and 7.99–188 ng/g dw, with PFPeA and PFDoA were the largest contributors in the two matrices. The highest PFAS levels were found in the Taihu Lake watershed, where textile manufacturing and metal plating activities highly prosper. With regard to the congener and isomer signatures, short-chain homologs dominated in soils (65.5%), whereas long-chain PFAS showed a major proportion in barks (41.9%). The composition of linear isomers of PFOS, PFOA and PFHxS implied that precursor degradation might be an important source of PFAS in addition to the 3M electrochemical fluorination (ECF). Additionally, the distance from the emission source, total organic carbon (TOC), logKOA and logKOW were considered potential influencing factors in PFAS distributions. Based on the multi-media fugacity model, about 71% of the fugacity fraction (ffs) values of the PFAS were below 0.3, indicating the dominant deposition from the atmosphere to the soil. The average fluxes of air-soil exchange for PFAS were −0.700 ± 11.0 ng/(m2·h). Notably, the estimated daily exposure to PFAS ranged from 9.57 × 10−2 to 8.59 × 10−1 ng/kg·bw/day for children and 3.31 × 10−2 to 3.09 × 10−1 ng/kg·bw/day for adults, suggesting low risks from outdoor inhalation and dermal uptake. Overall, results from distribution with structural diversity, air-soil exchange and preliminary risk assessment. This study provided in-depth insight of PFAS in multi-medium environment and bridged gaps between field data and policy-making for pollution control.

Durable water- and oil-repellent textiles without long- or short-chain perfluoroalkylated substances

For decades, the water and oil repellency of textiles was achieved using long-chain (CnF2n+1, n ≥ 7) perfluoroalkyl substances (PFAS). However, due to their proven bioaccumulative nature and toxic impacts on the environment and human health, these substances have been phased out of industrial production and/or legally banned in many countries. There is some evidence that a shorter carbon chain leads to less bioaccumulation and toxicity, and accordingly short-chain PFAS have been widely used as a replacement in recent years. Nevertheless, short-chain PFAS exhibit inferior surface properties due to their less crystalline and more loosely packed polymer chains, as compared to their long-chain counterparts. Moreover, surface properties become worse with decreasing chain length. Here we develop an alternative method for obtaining durable water and oil repellency on a nylon fabric using a liquidlike perfluoropolyether (PFPE) brush coating. The coating demonstrates excellent water and oil repellency, on par with the banned long-chain PFAS finishes, although its longest PFAS degradation product would have a chain length of L = 3, i.e. an ultra-short-chain PFAS. The PFPE-treated nylon exhibits superior surface properties compared to state-of-the-art, short-chain PFAS finished fabrics used in industry currently, even after laundering and 10,000 cycles of abrasion. The comfort of the treated fabrics is also maintained. The PFPE coatings developed here could replace the toxic, short-chain PFAS in use worldwide today.

Complex monitoring of perfluoroalkyl substances (PFAS) from tap drinking water in the Czech Republic

This study aims to quantify perfluoroalkyl substances (PFAS) in tap drinking water in the Czech Republic and to assess potential health risks to consumers using hazard ratios. A total of 192 samples (collected systematically throughout the country in 2021) were analysed for 28 PFAS using ultra-performance liquid chromatography with tandem mass spectrometry after solid phase extraction. Total PFAS (∑PFAS) concentrations ranged from undetectable to 23.9 ng/L. Long-chain PFAS (≥7 CF2 groups) were detected less frequently and at lower concentrations compared to short-chain (< 6 CF2 groups) homologues. Detectability and ∑PFAS concentrations in surface and combined water sources (median 2.97 ng/L) samples were higher than in groundwater sources (median 0.48 ng/L). With regard to the new Drinking Water Directive (EU 2020/2184), the parameter “sum of PFAS”, defined as the sum of 20 selected PFAS, was five times lower than the minimum acceptable dose in the most contaminated sample. The occurrence of PFAS in the Czech Republic is thus very low and comparable to other recent European studies. Consumption of any of the tested waters would not pose a moderate risk for adults, and only about 1% of the samples could pose a potential health risk.

Perfluoroalkyl substances in umbilical cord blood and blood pressure in offspring: a prospective cohort study

BackgroundHumans are widely exposed to perfluoroalkyl substances (PFAS), which have been found to be associated with various adverse birth outcomes. As blood pressure (BP) is an important parameter reflecting cardiovascular health in early life, it is necessary to investigate the association of PFAS exposure during early lifetime and BP in childhood. Therefore, we investigated the potential association between PFAS levels in umbilical cord blood and BP of the offspring at 4 years of age in a prospective cohort study.MethodsPFAS in umbilical cord blood samples after birth were measured with high-performance liquid chromatography/tandem mass spectrometry in the Shanghai Birth Cohort. BP was measured at 4 years of age in the offspring. Multiple linear regression model was used to investigate the association between individual PFAS level and BP of the offspring. Bayesian kernel machine regression (BKMR) was used to analyze the relationship between the PFAS mixture and BP of the offspring, while weighted quantile sum (WQS) regression was utilized for sensitivity analysis.ResultsA total of 129 mother-child pairs were included in our analysis. In multiple linear regressions, we observed that long-chain PFAS, mainly including perfluorooctane sulfonate (PFOS), perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUA), was negatively associated with systolic blood pressure (SBP), diastolic blood pressure (DBP) and mean arterial blood pressure (MAP). BKMR showed that an increase in umbilical cord blood PFAS mixture levels was significantly associated with a decrease in SBP, DBP and MAP [Estimated differences (SD): -0.433 (0.161); -0.437 (0.176); -0.382 (0.179), respectively]. The most important component in the association with SBP, DBP, and MAP was PFUA. PFDoA was found to be positively associated with SBP, DBP and MAP in both models. Sensitivity analysis with WQS regression showed consistent results.ConclusionOur findings suggested that umbilical blood PFAS exposure was negatively associated with BP in offspring at 4 years of age, including SBP, DBP, and MAP.

Biomagnification and temporal trends (1990–2021) of perfluoroalkyl substances in striped dolphins (Stenella coeruleoalba) from the NW Mediterranean sea

Poly- and Perfluoroalkyl Substances (PFAS) are a well-known class of pollutants which can bioaccumulate and biomagnify with a vast majority being highly persistent. This study aims to determine the biomagnification rates of PFAS in sexually mature striped dolphins and to assess temporal trends on PFAS concentrations over the past three decades (1990–2021) in the North-Western Mediterranean Sea. Thirteen and 17 of the 19 targeted PFAS were detected in the samples of the dolphins’ digestive content and liver, respectively, at concentrations ranging between 43 and 1609 ng/g wet weight, and 254 and 7010 ng/g wet weight, respectively. The most abundant compounds in both types of samples were linear perfluorooctanesulfonic acid (n-PFOS) and perfluorooctanesulfonamide (FOSA), which were present in all samples, followed by perfluoroundecanoic acid (PFUnDA), perfluorotridecanoic acid (PFTrDA) and perfluorononanoic acid (PFNA). Long-chain PFAS (i.e., PFCAs C ≥ 7 and PFSAs C ≥ 6) biomagnified to a greater extent than short-chain PFAS, suggesting a potential effect on the health of striped dolphins. Environmental Quality Standards concentrations set in 2014 by the European Union were exceeded in half of the samples of digestive content, suggesting that polluted prey may pose potential health risks for striped dolphins. Concentrations of most long-chain PFAS increased from 1990 to 2004–2009, then stabilized during 2014–2021, possibly following country regulations and industrial initiatives. The current study highlights the persistent presence of banned PFAS and may contribute to future ecological risk assessments and the design of management strategies to mitigate PFAS pollution in marine ecosystems.

Evaluation of the Effect of Perfluorohexane Sulfonate on the Proliferation of Human Liver Cells.

Perfluorohexane sulfonate (PFHxS) is a widely detected replacement for legacy long-chain perfluoroalkyl substances (PFAS) in the environment and human blood samples. Its potential toxicity led to its recent classification as a globally regulated persistent organic pollutant. Although animal studies have shown a positive association between PFHxS levels and hepatic steatosis and hepatocellular hypertrophy, the link with liver toxicity, including end-stage liver cancer, remains inconclusive. In this study, we examined the effects of PFHxS on the proliferation of Hep3B (human hepatocellular carcinoma) and SK-Hep1 (human liver sinusoidal endothelial cells). Cells were exposed to different PFHxS concentrations for 24-48 h to assess viability and 12-14 days to measure colony formation. The viability of both cell lines increased at PFHxS concentrations <200 μM, decreased at >400 μM, and was highest at 50 μM. Colony formation increased at <300 μM and decreased at 500 μM PFHxS. Consistent with the effect on cell proliferation, PFHxS increased the expression of proliferating cell nuclear antigen (PCNA) and cell-cycle molecules (CDK2, CDK4, cyclin E, and cyclin D1). In summary, PFHxS exhibited a biphasic effect on liver cell proliferation, promoting survival and proliferation at lower concentrations and being cytotoxic at higher concentrations. This suggests that PFHxS, especially at lower concentrations, might be associated with HCC development and progression.

Associations between perfluoroalkyl substances and the severity of non-alcoholic fatty liver disease

BackgroundNon-alcoholic fatty liver disease (NAFLD) has become the leading cause of chronic liver disease worldwide and the determinants driving its severity remain to be elucidated. Perfluoroalkyl substances (PFAS) are synthetic chemical compounds. They are used in commonplace products and persistent in water, soil and the human body. In vitro and animal studies suggest a pathogenic role for PFAS in metabolic diseases such as NAFLD. ObjectivesWe aimed to evaluate the association between NAFLD severity and serum PFAS concentrations in humans. MethodsOne hundred biopsy-proven NAFLD patients were included with a well-balanced distribution between the different stages of severity: 25 patients with simple steatosis, 25 with early non-alcoholic steatohepatitis (NASH and F0–F1 fibrosis), 33 with fibrotic NASH (NASH and F2–F3 fibrosis), and 17 with cirrhotic NASH (NASH and F4 fibrosis). Liver histological features were evaluated according to the NASH Clinical Research Network classification. Seventeen PFAS were measured by high-performance liquid chromatography coupled with tandem mass spectrometry on serum samples stored at −80 °C. ResultsThe median age was 60 years, 61 % of patients were male, 46 % had diabetes and the median body mass index (BMI) was 32 kg/m2. Long-chain PFAS were associated with steatosis grade (p = 0.03). Among the nine PFAS detected in > 50 % of the patients, Perfluoro-n-heptanoic acid (PFHpA) showed significantly higher concentrations in grade 3 steatosis versus grade 1 (p = 0.02). Perfluoro-n-dodecanoic acid (PFDoA) concentrations were higher in patients with significant fibrosis (p = 0.04) and PFHpA in patients with advanced fibrosis (p = 0.02). The association between PFHpA and steatosis grade remained significant in multivariate analysis adjusted for age, gender, BMI, diabetes presence and dyslipidemia (p = 0.004). DiscussionOur study showed a significant association between PFHpA and liver steatosis in NAFLD. According to data available in the literature, PFHpA could be implicated in liver steatosis through β-oxidation and biosynthesis of fatty acids.

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.

Concentration, distribution, and bioconcentration of short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a typical semi-enclosed bay

This study investigated per- and polyfluoroalkyl substances (PFAS) levels in the surface water, suspended particulate matter (SPM), sediment, and fishes in the Laizhou Bay (LZB) and its inflow river estuaries in dry, normal, and wet seasons. The results demonstrated that the short-chain perfluoroalkyl acids (PFAA) accounted for about 60 % of the total PFAA (∑PFAA) concentration in water, while long-chain PFAA were the dominant compounds in the sediment and SPM. The levels of the ∑PFAA and their precursors decreased from the estuaries to the bay, which implied that terrigenous input (pollutant in land flowed into sea) was the main pollution source of PFAA in the LZB. The PFAAs levels in surface water were ranked as the order of dry > normal > wet season. The distribution coefficients of PFAA showed that the long-chain PFAA were more prone to be adsorbed by sediment and SPM than short-chain PFAA. The increase of ∑PFAA concentrations was in the range of 0.32–36.7 ng·L−1 after the oxidation conversion of water samples. Precursors were the important source of the PFAA in the surface water. The perfluorooctane sulfonate (PFOS) was the dominant compound in fish tissues. These results provide hints for understanding PFAS pollution in LZB.

Periodically reversing electrocoagulation technique for efficient removal of short-chain perfluoroalkyl substances from contaminated groundwater around a fluorochemical facility

Widespread distributions of short-chain perfluoroalkyl substances (PFASs) has been recognized as a crucial environmental issue. However, multiple treatment techniques were ineffective due to their high polarity and mobility, contributing to a never-ending existence in the aquatic environment ubiquitously. The present study revealed potential technique of periodically reversing electrocoagulation (PREC) to perform efficient removal of short-chain PFASs including experimental factors (in the conditions of 9 V for voltage, 600 r/min of stirring speed, 10 s of reversing period, and 2 g/L of NaCl electrolyte), orthogonal experiments, actual application, and removal mechanism. Accordingly, based upon the orthogonal experiments, the removal efficiencies of perfluorobutane sulfonate (PFBS) in simulated solution could achieve 81.0% with the optimal parameters of Fe–Fe electrode materials, addition of 665 μL H2O2 per 10 min, and pH at 3.0. The PREC was further applied for treating the actual groundwater around a fluorochemical facility, consequently the removal efficiencies for typical short-chain perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), PFBS, and perfluoropentane sulfonate (PFPeS) were 62.5%, 89.0%, 96.4%, 90.0%, and 97.5%, respectively. The other long-chain PFASs contaminants had superior removal with the removal efficiencies up to 97%–100%. In addition, a comprehensive removal mechanism related to electric attraction adsorption for short-chain PFASs could be verified through the morphological analysis of ultimate flocs composition. The oxidation degradation was further revealed as the other removal mechanism by suspect and nontarget screening of intermediates formed in simulated solution, as well as density functional theory (DFT) calculation theory. Moreover, the degradation pathways about one CF2O molecule or CO2 eliminated with one C atom removed in PFBS by ·OH generated from the PREC oxidation process were further proposed. As a result, the PREC would be a promising technique for the efficient removal of short-chain PFASs from severely contaminated water bodies.

Adsorption behavior of long-chain perfluoroalkyl substances on hydrophobic surface: A combined molecular characterization and simulation study

Hydrophobic interaction is a prevalent sorption mechanism of poly- and perfluoroalkyl substances (PFAS) in natural and engineered environments. In this study, we combined quartz crystal microbalance with dissipation (QCM-D), atomic force microscope (AFM) with force mapping, and molecular dynamics (MD) simulation to probe the molecular behavior of PFAS at the hydrophobic interface. On a CH3-terminated self-assembled monolayer (SAM), perfluorononanoic acid (PFNA) showed ∼2-fold higher adsorption than perfluorooctane sulfonate (PFOS) that has the same fluorocarbon tail length but a different head group. Kinetic modeling using the linearized Avrami model suggests that the PFNA/PFOS-surface interaction mechanisms can evolve over time. This is confirmed by AFM force-distance measurements, which shows that while the adsorbed PFNA/PFOS molecules mostly lay flat, a portion of them formed aggregates/hierarchical structures of 1–10 nm in size after lateral diffusion on surface. PFOS showed a higher affinity to aggregate than PFNA. Association with air nanobubbles is observed for PFOS but not PFNA. MD simulations further showed that PFNA has a greater tendency than PFOS to have its tail inserted into the hydrophobic SAM, which can enhance adsorption but limit lateral diffusion, consistent with the relative behavior of PFNA/PFOS in QCM and AFM experiments. This integrative QCM-AFM-MD study reveals that the interfacial behavior of PFAS molecules can be heterogeneous even on a relatively homogeneous surface.

Investigating the Electrochemically Driven Capture and Release of Long-Chain PFAS by Redox Metallopolymer Sorbents.

The remediation of perfluoroalkyl substances (PFAS) is an urgent challenge due to their prevalence and persistence in the environment. Electrosorption is a promising approach for wastewater treatment and water purification, especially through the use of redox polymers to control the binding and release of target contaminants without additional external chemical inputs. However, the design of efficient redox electrosorbents for PFAS faces the significant challenge of balancing a high adsorption capacity while maintaining significant electrochemical regeneration. To overcome this challenge, we investigate redox-active metallopolymers as a versatile synthetic platform to enhance both electrochemical reversibility and electrosorption uptake capacity for PFAS removal. We selected and synthesized a series of metallopolymers bearing ferrocene and cobaltocenium units spanning a range of redox potentials to evaluate their performance for the capture and release of perfluorooctanoic acid (PFOA). Our results demonstrate that PFOA uptake and regeneration efficiency increased with more negative formal potential of the redox polymers, indicating possible structural correlations with the electron density of the metallocenes. Poly(2-(methacryloyloxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF6) showed the highest affinity toward PFOA, with an uptake capacity of more than 90 mg PFOA/g adsorbent at 0.0 V vs Ag/AgCl and a regeneration efficiency of more than 85% at -0.4 V vs Ag/AgCl. Kinetics of PFOA release showed that electrochemical bias greatly enhanced the regeneration efficiency when compared to open-circuit desorption. In addition, electrosorption of PFAS from different wastewater matrices and a range of salt concentrations demonstrated the capability of PFAS remediation in complex water sources, even at ppb levels of contaminants. Our work showcases the synthetic tunability of redox metallopolymers for enhanced electrosorption capacity and regeneration of PFAS.

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.

Microbial biotransformation mechanisms of PFPiAs in soil unveiled by metagenomic analysis

As alternatives of long-chain PFASs (Poly- and perfluoroalkyl substances), perfluoroalkyl phosphinic acids (PFPiAs) are increasingly observed in the environment, but their environmental behaviors have not been well understood. Here, the microbial biotransformation of C6/C6 and C8/C8 PFPiA in two soils (Soil N and Y) was investigated. After 252 d and 330 d of incubation with PFPiAs in Soil N and Y respectively, the levels of PFPiAs decreased distinctly, accompanied by the increasing perfluorohexaphosphonic acid (PFHxPA) or perfluorooctanophosphonic acid (PFOPA) formation, magnifying PFPiAs were susceptible to C-P cleavage, which was also confirmed by the density functional theory calculations. The half-lives of the PFPiAs were longer than one year, while generally shorter in Soil N than in Soil Y and that of C6/C6 was shorter than C8/C8 PFPiA (392 d and 746 d in Soil N, and 603 and 1155 d in Soil Y, respectively). Metagenomic sequencing analysis revealed that Proteobacteria as the primary host of the potential functional genes related to CP bond cleavage might be the crucial phyla contributing to the biotransformation of PFPiAs. Meanwhile, the more intensive interactions between the microbes in Soil N consistently contribute to its greater capacity for transforming PFPiAs.

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.

Circular economy in wastewater treatment plants: Treatment of contaminants of emerging concerns (CECs) in effluent using sludge-based activated carbon

Contaminants of Emerging Concern (CECs), including polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and poly and perfluoroalkyl substances (PFASs), have been frequently detected at high concentrations in discharged wastewater effluents and biosolids. This study investigates the occurrence and removal of various PAHs, PFASs, and PBDEs from the final discharge effluent of a major Canadian wastewater treatment plant. We evaluated two seasons of the year (warm and cold) (effluents A and B) using sludge-based activated carbon (SBAC) samples synthesised from thickened waste secondary sludge and biosolids, named TS-SBAC and BioSBAC, respectively. The average removal efficiency of BioSBAC (at concentrations of 1 and 10 g SBAC in 1-L effluent) for PAHs and alkyl-PAHs in effluent A was 88–100% (residual concentrations below the reporting limit [RL] at 16.7 ng/L), and that of TS-SBAC (concentration of 1 g SBAC in 1-L effluent) in effluent B (below RL, at 20.8 ng/L) was 68–100%. The average removal efficiency of BioSBAC for PBDEs was 88–100% for effluent A (below RL, at 1.26 ng/L), and that of TS-SBAC for effluent B (below RL, at 1.14 ng/L) was 52–100%. The average BioSBAC removal range of PFASs from effluent B (below RL, at 5.37 ng/L) was 30–100%, with significant removal of long-chain (>C7) PFASs. These findings indicate that producing an efficient adsorbent (i.e., SBAC) from sewage sludge is a sustainable integrated circular economy solution for stabilising CECs, including PAHs, PFASs, and PBDEs, to improve the quality of wastewater effluents in a closed-loop system, with no waste being generated.

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.