Short-chain Polyfluoroalkyl Substances Research Articles

Spatial distribution, source, and fate of per- and polyfluoroalkyl substances in the surrounding environment of closed and converted fluorochemical factories in Fujian, China

Following the closure of perfluorooctanesulfonic acid (PFOS) production to comply with the Stockholm Convention regulations or restrictions, manufacturers have shifted to developing short-chain alternatives like perfluorobutane sulfonic acid (PFBS). However, limited research has been conducted to evaluate the impact of this transition on the surrounding environment. This study focused on the spatial distribution, source, and fate of 18 per- and polyfluoroalkyl substances (PFAS) in the surrounding environment of the closure and transformation of two PFAS manufacturing plants in Fujian, China. The total concentrations of PFAS in surface water, sediment, and fish were within the range of 48.9–72,400 ng/L, 0.930–57.6 ng/g dw, and 3.33–1245 ng/g dw, respectively. The predominant compounds were PFBS, PFOS, and perfluorooctanoic acid (PFOA) among the three matrices. Principal component analysis highlighted significant differences in PFAS profiles across different regions of the Futun River, suggesting diverse sources of PFAS. Source apportionment indicated that despite being closed or converted for almost three years, the two factories still significantly impacted the surrounding environment. The shutdown factory mainly released PFAS characterized by perfluoroalkyl sulfonic acids. In contrast, the PFAS were released from conversion plant with the fingerprint being PFBS and perfluoroalkyl carboxylic acids. The conversion of the factories has resulted in the coexistence of long-chain and short-chain PFAS, which has complicated the composition of PFAS in the environment. As sewage treatment plant could not effectively remove PFBS and perfluorobutanoic acid (PFBA) in wastewater, and due to their strong migration ability, these chemicals had a wider impact range, increasing the difficulty of environmental restoration and management. Risk assessment showed that PFAS downstream of the two factories posed high or moderate ecological risks. Specifically, PFBS, PFOS, and PFOA displayed the highest risk quotients and should be paid further attention.

Remove legacy perfluoroalkyl acids and emerging per- and polyfluoroalkyl ether acids by single-use and regenerable anion exchange resins: Rapid small-scale column tests and model fits

Rapid small-scale column tests (RSSCT) are used to study the removal of per- and polyfluoroalkyl substances (PFAS) for drinking water treatment by ion exchange. Breakthroughs of 15 emerging per- and perfluoroalkyl ether acids and six legacy perfluoroalkyl acid analogs are studied using a single-use PFAS-selective anion exchange resin (AER1) and a regenerable, generic anion exchange resin (AER2). The Bohart-Adams model was used to describe and predict breakthrough, with the modeled results reasonably aligned with RSSCT results in most cases, enabling shorter RSSCT duration for future applications. AER1 exhibited high uptake capacity with no breakthrough for 11 of the 21 tested PFAS during the 144,175 BV continuous operation, allowing compliance with the new National Primary Drinking Water Regulation in many application scenarios. AER2 exhibited much faster breakthroughs for most PFAS and is not a promising option for drinking water treatment. However, the summed PFAS capacity via model fit and total PFAS adsorbed via measurement were only <0.01 % of both resin capacities at full breakthrough, suggesting PFAS could only occupy a tiny portion of the ion exchange sites even for the PFAS-selective AER1. Ether group insertion in the PFAS group leads to later breakthrough, and linear isomers were better captured by the resins than the branched isomers. Overall, PFAS uptake capacity increases and kinetics decrease when the PFAS molecular volume increases. Regeneration using 10 % NaCl solutions partially released PFAS from AER2 but not from AER1, with more short-chain PFAS released than long-chain ones. Ether group insertion decreased the PFAS recoveries during the regeneration of AER2. The regenerated resins showed much faster breakthroughs than the pristine resins, making them unfavorable for drinking water treatment applications. Adsorption displacement of short-chain PFAS by long-chain PFAS was observed in pristine AER1, and post-regeneration leaching occurred for both resins, both phenomena making the resins a possible PFAS source in long-term use.

Treatment of aqueous per- and poly-fluoroalkyl substances: A review of biochar adsorbent preparation methods

Per- and poly-fluoroalkyl substances (PFAS) are synthetic chemicals widely used in everyday products, causing elevated concentrations in drinking water and posing a global challenge. While adsorption methods are commonly employed for PFAS removal, the substantial cost and environmental footprint of commercial adsorbents highlight the need for more cost-effective alternatives. Additionally, existing adsorbents exhibit limited effectiveness, particularly against diverse PFAS types, such as short-chain PFAS, necessitating modifications to enhance adsorption capacity. Biochar can be considered a cost-effective and eco-friendly alternative to conventional adsorbents. With abundant feedstocks and favorable physicochemical properties, biochar shows significant potential to be applied as an adsorbent for removing contaminants from water. Despite its effectiveness in adsorbing different inorganic and organic contaminants from water environments, some factors restrict its effective application for PFAS adsorption. These factors are related to the biochar properties, and characteristics of PFAS, as well as water chemistry. Therefore, some modifications have been introduced to overcome these limitations and improve biochar's adsorption capacity. This review explores the preparation conditions, including the pyrolysis process, activation, and modification techniques applied to biochar to enhance its adsorption capacity for different types of PFAS. It addresses critical questions about the adsorption performance of biochar and its composites, mechanisms governing PFAS adsorption, challenges, and future perspectives in this field. The surge in research on biochar for PFAS adsorption indicates a growing interest, making this timely review a valuable resource for future research and an in-depth exploration of biochar's potential in PFAS remediation.

Exposure to per- and polyfluoroalkyl substances in lung cancer patients and their associations with clinical health indicators

Per- and polyfluoroalkyl substances (PFASs) have potential carcinogenicity, immunotoxicity, and hepatotoxicity. Research has been conducted on PFAS exposure in people to discuss their potential health effects, excluding lung cancer. In this study, we recruited participants (n = 282) with lung cancer from Heilongjiang Province, northeast China. The PFAS concentrations were measured in their serum to fill the data gap of exposure, and relationships were explored in levels between PFASs and clinical indicators of tumor, immune and liver function. Ten PFASs were found in over 80 % of samples and their total concentrations were 5.27–152 ng/mL, with the highest level for perfluorooctanesulfonate (median: 12.4 ng/mL). Long-chain PFASs were the main congeners and their median concentration (20.5 ng/mL) was nearly three times to that of short-chain PFASs (7.61 ng/mL). Significantly higher concentrations of perfluorobutanoic acid, perfluorononanoic acid and perfluorohexanesulfonate were found in males than in females (p < 0.05). Serum levels of neuro-specific enolase were positively associated with perfluoropentanoic acid in all participants and were negatively associated with perfluorononanesulfonate in females (p < 0.05, multiple linear regression models). Exposure to PFAS mixture was significantly positively associated with the lymphocytic absolute value (difference: 0.224, 95% CI: 0.018, 0.470; p < 0.05, quantile g-computation models) and serum total bilirubin (difference: 2.177, 95% CI: 0.0335, 4.33; p < 0.05). Moreover, PFAS exposure can affect γ-glutamyl transpeptidase through several immune markers (p < 0.05, mediating test). Our results suggest that exposure to certain PFASs could interfere with clinical indicators in lung cancer patients. To our knowledge, this is the first study to detect serum PFAS occurrence and check their associations with clinical indicators in lung cancer patients.

Commercial compost amendments inhibit the bioavailability and plant uptake of per- and polyfluoroalkyl substances in soil-porewater-lettuce systems

Compost is widely used in agriculture as fertilizer while providing a practical option for solid municipal waste disposal. However, compost may also contain per- and polyfluoroalkyl substances (PFAS), potentially impacting soils and leading to PFAS entry into food chains and ultimately human exposure risks via dietary intake. This study examined how compost affects the bioavailability and uptake of eight PFAS (two ethers, three fluorotelomer sulfonates, and three perfluorosulfonates) by lettuce (Lactuca sativa) grown in commercial organic compost-amended, PFAS spiked soils. After 50 days of greenhouse experiment, PFAS uptake by lettuce decreased (by up to 90.5 %) with the increasing compost amendment ratios (0–20 %, w/w), consistent with their decreased porewater concentrations (by 30.7–86.3 %) in compost-amended soils. Decreased bioavailability of PFAS was evidenced by the increased in-situ soil-porewater distribution coefficients (Kd) (by factors of 1.5–7.0) with increasing compost additions. Significant negative (or positive) correlations (R2 ≥ 0.55) were observed between plant bioaccumulation (or Kd) and soil organic carbon content, suggesting that compost amendment inhibited plant uptake of PFAS mainly by increasing soil organic carbon and enhancing PFAS sorption. However, short-chain PFAS alternatives (e.g., perfluoro-2-methoxyacetic acid (PFMOAA)) were effectively translocated to shoots with translocation factors > 2.9, increasing their risks of contamination in leafy vegetables. Our findings underscore the necessity for comprehensive risk assessment of compost-borne PFAS when using commercial compost products in agricultural lands.

Occurrence of forever chemicals in Chennai waters, India

BackgroundPer- and polyfluoroalkyl substances (PFAS) are considered ‘contaminants of emerging concern’ due to their environmental persistence, bio-accumulative potential, and adverse effects on human health. They are widely employed in producing various goods used in daily life, such as non-stick cookware, cleaning agents, and many industrial applications in aerospace, automotive, construction, electronics, and military, all of which ultimately end up in different environmental matrices. India’s rapid economic growth necessitates a comprehensive understanding of its PFAS contamination levels and potential human and ecological exposure.ResultsThe present study reports the quantification of one long-chain and two short-chain perfluoroalkyl acids and three long-chain and two short-chain perfluorosulfonic acids and qualitative analysis using suspect screening in the waters of Chennai, Tamil Nadu, India. Samples were collected from surface and groundwater sources, including the Adyar river, Buckingham canal, Chembarambakkam lake, and the water treatment plant. The concentrations analyzed in all the samples ranged from 0.10 ng/L to 136.27 ng/L. Groundwater had some of the highest concentrations of PFAS. L-PFBS (up to 136.27 ng/L) and PFOA (up to 77.61 ng/L) are present in all the samples. The concentrations of all the target PFAS increased in the 5 to 103% range in the final treated water compared to the raw water of the water treatment plant. This treated water is distributed as a source of drinking water for the residents of Chennai. Additionally, the dominance of short-chain compounds (4–7 carbons) over long-chain compounds (> 7 carbons) was observed. Suspect screening revealed numerous precursors and other fluorinated compounds abundantly present in the samples.ConclusionsOur study revealed PFAS levels up to 136.27 ng/L in both surface and groundwater samples from Chennai. These findings raise concerns about potential risks to ecosystems and human well-being. The dominance of short-chain PFAS coupled with abundant precursors and unidentified fluorinated compounds indicates an ongoing shift toward alternatives. Conventional water treatment is ineffective in eliminating these chemicals from the water system; rather, increasing the PFAS concentrations from raw water to treated water necessitates advanced polishing steps. Industrial emissions, untreated domestic wastewater discharge, and open dump sites have been suspected as the significant sources of contamination, highlighting the need for further investigation to fully assess the extent of PFAS contamination in Chennai.Graphical

Using the benzenepolycarboxylic acid (BPCA) method to assess activated biochars and their PFAS sorption abilities

Activated carbon (AC) has important industrial and environmental applications as it has excellent abilities to sorb contaminants such as per- and polyfluoroalkyl substances (PFAS). Current research aims to develop activated biochars (AB) from renewable biomass to replace AC that is produced from fossil feedstock. Both AC and AB are primarily comprised of condensed aromatic carbon (ConAC), the component that is the focus of this study. ConAC is characterized to determine its relationship with biochar activation conditions and PFAS sorption, which are understudied at present.Benzenepolycarboxylic acid (BPCA) markers for ConAC were quantified in steam-activated biochars (AB-Steam) and carbon dioxide-activated biochars (AB-CO2) prepared from waste timber at different temperatures (800, 850, 900 °C) and molar ratios of feedstock-carbon:steam (0.50 – 1.25). A non-activated biochar was also included as a reference. ConAC relative to total organic carbon content was higher in AB-Steam than in AB-CO2 (92 ± 2 % vs. 81 ± 11%). The ratio of benzenehexa- (B6CA) to benzenepentacarboxylic (B5CA) acids revealed that AB-Steam also had larger ConAC clusters than AB-CO2. These findings provide novel evidence that steam activation is more effective than CO2 activation in creating ConAC.To assess how ConAC impacts AB sorption abilities, AB-Steam were used to remediate PFAS from contaminated soils. The observed strong correlations between ConAC content and sorption of long-chain PFAS suggest the importance of hydrophobic interactions between PFAS tails and ConAC. Poor correlations for short-chain PFAS, on the other hand, indicated the existence of electrostatic repulsion interactions between PFAS head groups and ConAC. Collectively, these results explain the great ability of AB-Steam to sorb PFAS from contaminated soils (up to 100% remediation). More broadly, this work demonstrates that the BPCA method can be a valuable tool to assess the quality of biochars and other carbonaceous sorbents in relation to their production conditions or contaminant sorption abilities.

Roles of varying carbon chains and functional groups of legacy and emerging per-/polyfluoroalkyl substances in adsorption on metal-organic framework: Insights into mechanism and adsorption prediction

Metal-organic frameworks (MOFs) are promising adsorbents for legacy per-/polyfluoroalkyl substances (PFASs), but they are being replaced by emerging PFASs. The effects of varying carbon chains and functional groups of emerging PFASs on their adsorption behavior on MOFs require attention. This study systematically revealed the structure-adsorption relationships and interaction mechanisms of legacy and emerging PFASs on a typical MOF MIL-101(Cr). It also presented an approach reflecting the average electronegativity of PFAS moieties for adsorption prediction. We demonstrated that short-chain or sulfonate PFASs showed higher adsorption capacities (μmol/g) on MIL-101(Cr) than their long-chain or carboxylate counterparts, respectively. Compared with linear PFASs, their branched isomers were found to exhibit a higher adsorption potential on MIL-101(Cr). In addition, the introduction of ether bond into PFAS molecule (e.g., hexafluoropropylene oxide dimeric acid, GenX) increased the adsorption capacity, while the replacement of CF2 moieties in PFAS molecule with CH2 moieties (e.g., 6:2 fluorotelomer sulfonate, 6:2 FTS) caused a decrease in adsorption. Divalent ions (such as Ca2+ and SO42−) and solution pH have a greater effect on the adsorption of PFASs containing ether bonds or more CF2 moieties. PFAS adsorption on MIL-101(Cr) was governed by electrostatic interaction, complexation, hydrogen bonding, π-CF interaction, and π-anion interaction as well as steric effects, which were associated with the molecular electronegativity and chain length of each PFAS. The average electronegativity of individual moieties (named Me) for each PFAS was estimated and found to show a significantly positive correlation with the corresponding adsorption capacity on MIL-101(Cr). The removal rates of major PFASs in contaminated groundwater by MIL-101(Cr) were also correlated with the corresponding Me values. These findings will assist with the adsorption prediction for a wide range of PFASs and contribute to tailoring efficient MOF materials.

Application of electron beam technology to decompose per- and polyfluoroalkyl substances in water

The widespread detection of per- and polyfluoroalkyl substances (PFAS) in environmental compartments across the globe has raised several health concerns. Destructive technologies that aim to transform these recalcitrant PFAS into less toxic, more manageable products, are gaining impetus to address this problem. In this study, a 9 MeV electron beam accelerator was utilized to treat a suite of PFAS (perfluoroalkyl carboxylates: PFCAs, perfluoroalkyl sulfonates, and 6:2 fluorotelomer sulfonate: FTS) at environmentally relevant levels in water under different operating and water quality conditions. Although perfluorooctanoic acid and perfluorooctane sulfonic acid showed >90% degradation at <500 kGy dose at optimized conditions, a fluoride mass balance revealed that complete defluorination occurred only at/or near 1000 kGy. Non-target and suspect screening revealed additional degradation pathways differing from previously reported mechanisms. Treatment of PFAS mixtures in deionized water and groundwater matrices showed that FTS was preferentially degraded (∼90%), followed by partial degradation of long-chain PFAS (∼15–60%) and a simultaneous increase of short-chain PFAS (up to 20%) with increasing doses. The increase was much higher (up to 3.5X) in groundwaters compared to deionized water due to the presence of PFAS precursors as confirmed by total oxidizable precursor (TOP) assay. TOP assay of e-beam treated samples did not show any increase in PFCAs, confirming that e-beam was effective in also degrading precursors. This study provides an improved understanding of the mechanism of PFAS degradation and revealed that short-chain PFAS are more resistant to defluorination and their levels and regulation in the environment will determine the operating conditions of e-beam and other PFAS treatment technologies.

Experimental and density functional theory investigation of surface-modified biopolymer for improved adsorption of mixtures of per- and polyfluoroalkyl substances in water

Glutaraldehyde (GTH) cross-linked chitosan (CTN) biopolymer-based and polyethyleneimine (PEI) functionalized (GTHCTNPEI) aerogels were proven promising for removing mixtures of long- and short chain per- and polyfluoroalkyl substances (PFAS) in water. In this study, to further improve the performance of the aerogel for short-chain PFAS and undecafluoro-2-methyl-3-oxahexanoic acid (GenX) removal, GTHCTNPEI aerogel chunks with an average size of 13.4 mm were turned into flakes with an average size of 9.1 mm. The GTHCTNPEI flakes achieved >99 % removal of all target PFAS, including long- and short-chain PFAS and >97 % for GenX after 10 h. In addition, the flakes can be regenerated and reused for at least four cycles. When added to tap water spiked with PFAS at initial concentrations of 30, 70, or 100 ng/L, the flakes removed almost 100 % of all tested PFAS. Mechanistic investigations using density functional theory (DFT) revealed strong stabilizing hydrophobic and electrostatic interactions between the aerogels and PFAS, with GTHCTNPEI to PFAS binding energies ranging between -24.0 – -30.1 kcal/mol for PFOA; -41.3 – -48.5 kcal/mol for PFOS; and -40.5 – -47.3 kcal/mol for PFBS. These results demonstrate the great potential of the flakes for removing PFAS from drinking water, surface water, and groundwater.

Degradation of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in water by use of a nonthermal plasma-ozonation cascade reactor: Role of different processes and reactive species

The widespread use of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the last century has caused serious pollution of water bodies around the world, threatening the health of humans and other organisms. In this work, a novel cascade reactor configuration, comprised of a dielectric barrier discharge (DBD) plasma chamber connected with an ozonation chamber was used to treat municipal secondary effluent loaded with several PFAS. The electrical energy per order (EE/O) for degradation of perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA) amounts 180 and 100 kWh/m3, respectively. While the short-chain PFAS (perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA)) were difficult to be degraded, i.e. degradation percentage < 32 % after 60 min, 80–90 % of the longer PFAS (PFOA and PFDA) were degraded within 60 min. The degradation of PFAS mainly occurred in the plasma chamber rather than in ozonation chamber. This is because that reductive species produced in plasma chamber, such as hydrated electrons (eaq−) and Ar+, played a direct role in defluorination, while oxidative species, including OH, O, O2−, 1O2, O3, and H2O2, has a very limited contribution for defluorination. Enhancing the utilization of reductive species is crucial to degrade PFAS. Perfluoroalkyl carboxylic acids (PFCA) generated during the plasma reactions may have a potential risk for environment. As such, further optimization should focus on full mineralization. This study provides an approach to solve the problem of PFAS-contaminated wastewater, which is of the importance to promote the application of nonthermal plasma technique in water treatment.

Fate of perfluoroalkyl and polyfluoroalkyl substances (PFAS) through two full-scale wastewater sludge incinerators.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are an emerging issue in wastewater treatment. High-temperature thermal processes, incineration being time-tested, offer the opportunity to destroy and change the composition of PFAS. The fate of PFAS has been documented through wastewater sludge incinerators, including a multiple hearth furnace (MHF) and a fluidized bed furnace (FBF). The dewatered wastewater sludge feedstock averaged 247- and 1280-μmol targeted PFAS per sample run in MHF and FBF feed, respectively. Stack emissions (reportable for all targeted PFAS from MHF only) averaged 5% of that value with shorter alkyl chain compounds comprising the majority of the targeted PFAS. Wet scrubber water streams accumulated nonpolar fluorinated organics from the furnace exhaust with an average of 0.740- and 0.114-mol F- per sample run, for the MHF and FBF, respectively. Simple alkane PFAS measured at the stack represented 0.5%-4.5% of the total estimated facility greenhouse gas emissions. PRACTITIONER POINTS: The MHF emitted six short chain PFAS from the stack, which were shorter alkyl chain compounds compared with sludge PFAS. The FBF did not consistently emit reportable PFAS from the stack, but contamination complicated the assessment. Five percent of the MHF sludge molar PFAS load was reported in the stack. MHF and FBF wet scrubber water streams accumulated nonpolar fluorinated organics from the furnace exhaust. Ultra-short volatile alkane PFAS measured at the stack represented 0.5%-4.5% of the estimated facility greenhouse gas emissions.

Unveiling per- and polyfluoroalkyl substance contamination in Chinese paper products and assessing their exposure risk

The contamination characteristics, migration patterns and health risks of per- and polyfluoroalkyl substances (PFAS) were investigated in 66 Chinese paper products by using target and non-target screening methods. Among 57 target PFASs, 5 and 6 PFASs were found in the hygiene paper products (<LOQ-12.6 ng/g) and stationery paper products (<LOQ-8.8 ng/g), respectively. A total of 25 PFASs were detected in the 39 food contact paper products, with the highest concentration of 1630 ng/g. Suspect and non-target analysis have found 28 PFASs with confidence levels 1–3, 132 certain PFAS compounds (level 4) and 56 homologue groups (level 5), containing newly identified long-chain polyfluorocarboxylic acid (9:3/11:3FTCA, 11:3/13:3FTUCA) and X:2 FTOH-Sulfate. A potential transformation relationship between the detected PFAS was proposed, starting from X:2 FTOH and finally transforming to CnF2n+1COOH. Microwave heating can increase the release of PFAS in popcorn bags and convert long-chain PFAS into short-chain ones. The migration experiments indicated that the ethanol in food simulants can increase the migration of PFAS, and short-chain PFAS exhibits a greater migration trend. The estimated daily intake (EDI) values for 6 of 18 paper bowls/plates exceeded the recommendation of 0.63 ng/kg bw/day by the European Food Safety Authority (EFSA), posing a potential threat to human health.

Dynamic spatiotemporal changes of per- and polyfluoroalkyl substances (PFAS) in soil and eggs of private gardens at different distances from a fluorochemical plant

Homegrown food serves as an important human exposure source of per- and polyfluoroalkyl substances (PFAS), yet little is known about their spatiotemporal distribution within and among private gardens. This knowledge is essential for more accurate site-specific risk assessment, identification of new sources and evaluating the effectiveness of regulations. The present study evaluated spatiotemporal changes of legacy and emerging PFAS in surface soil from vegetable gardens (N = 78) and chicken enclosures (N = 102), as well as in homegrown eggs (N = 134) of private gardens, across the Province of Antwerp (Belgium). Hereby, the potential influence of the wind orientation and distance towards a major fluorochemical plant was examined. The ∑short-chain PFAS and precursor concentrations were higher in vegetable garden soil (8.68 ng/g dry weight (dw)) compared to chicken enclosure soil (4.43 ng/g dw) and homegrown eggs (0.77 ng/g wet weight (ww)), while long-chain sulfonates and C11−14 carboxylates showed the opposite trend. Short-term (2018/2019–2022) changes were mostly absent in vegetable garden soil, while changes in chicken enclosure soils oriented S-SW nearby (<4 km) the fluorochemical plant were characterized by a local, high-concentration plume. Moreover, soil from chicken enclosures oriented SE and remotely from the plant site was characterized by a widespread, diffuse but relatively low-concentration plume. Long-term data (2010–2022) suggest that phaseout and regulatory measures have been effective, as PFOS concentrations nearby the fluorochemical plant in soil and eggs have declined from 25.8 to 2.86 ng/g dw and from 528 to 39.4 ng/g ww, respectively. However, PFOS and PFOA concentrations have remained largely stable within this timeframe in gardens remotely from the plant site, warranting further rapid regulation and remediation measures. Future monitoring efforts are needed to allow long-term comparison for multiple PFAS and better distinction from potential confounding variables, such as variable emission outputs and variability in wind patterns.

Stabilization of PFAS-contaminated soil with sewage sludge- and wood-based biochar sorbents

Sustainable and effective remediation technologies for the treatment of soil contaminated with per- and polyfluoroalkyl substances (PFAS) are greatly needed. This study investigated the effects of waste-based biochars on the leaching of PFAS from a sandy soil with a low total organic carbon content (TOC) of 0.57 ± 0.04 % impacted by PFAS from aqueous film forming foam (AFFF) dispersed at a former fire-fighting facility. Six different biochars (pyrolyzed at 700–900 °C) were tested, made from clean wood chips (CWC), waste timber (WT), activated waste timber (aWT), two digested sewage sludges (DSS-1 and DSS-2) and de-watered raw sewage sludge (DWSS). Up-flow column percolation tests (15 days and 16 pore volume replacements) with 1 % biochar indicated that the dominant congener in the soil, perfluorooctane sulphonic acid (PFOS) was retained best by the aWT biochar with a 99.9 % reduction in the leachate concentration, followed by sludge-based DWSS (98.9 %) and DSS-2 and DSS-1 (97.8 % and 91.6 %, respectively). The non-activated wood-based biochars (CWC and WT) on the other hand, reduced leaching by <42.4 %. Extrapolating this to field conditions, 90 % leaching of PFOS would occur after 15 y for unamended soil, and after 1200 y and 12,000 y, respectively, for soil amended with 1 % DWSS-amended and aWT biochar. The high effectiveness of aWT and the three sludge-based biochars in reducing PFAS leaching from the soil was attributed largely to high porosity in a pore size range (>1.5 nm) that can accommodate the large PFAS molecules (>1.02–2.20 nm) combined with a high affinity to the biochar matrix. Other factors like anionic exchange capacity could play a contributing role. Sorbent effectiveness was better for long-chain than for short-chain PFAS, due to weaker, apolar interactions between the biochar and the latter's shorter hydrophobic CF2-tails. The findings were the first to demonstrate that locally sourced activated wood-waste biochars and non-activated sewage sludge biochars could be suitable sorbents for the ex situ stabilization and in situ remediation of PFAS-contaminated soil, bringing this technology one step closer to full-scale field testing.

PFAS promotes disinfection byproduct formation through triggering particle-bound organic matter release in drinking water pipes

Loose deposit particles in drinking water distribution system commonly exist as mixtures of metal oxides, organic materials, bacteria, and extracellular secretions. In addition to their turbidity-causing effects, the hazards of such particles in drinking water are rarely recognized. In this study, we found that trace per- and polyfluoroalkyl substances (PFASs) could dramatically promote the formation of disinfection byproducts (DBPs) by triggering the release of particle-bound organic matter. Carboxylic PFASs have a greater ability to increase chloroacetic acid than sulfonic PFASs, and PFASs with longer chains have a greater ability to increase trichloromethane release than shorter-chain PFASs. Characterization by organic carbon and organic nitrogen detectors and Fourier transform ion cyclotron resonance mass spectrometry revealed that the released organic matter was mainly composed of proteins, carbohydrates, lignin, and condensed aromatic structures, which are the main precursors for the formation of DBPs, particularly highly toxic aromatic DBPs. After the release of organic matter, the particles exhibit a decrease in surface functional groups, an increase in surface roughness, and a decrease in particle size. The findings provide new insights into the risks of loose deposits and PFASs in drinking water, not only on PFASs per se but also on its effect of increasing toxic DBPs.

Characterizing Volatile Emissions and Combustion Byproducts from Aqueous Film-Forming Foams Using Online Chemical Ionization Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m-3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger (C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.

Metal-Organic Framework-Based Composites for the Adsorption Removal of Per- and Polyfluoroalkyl Substances from Water.

The increasing health risks posed by per- and polyfluoroalkyl substances (PFASs) in the environment highlight the importance of implementing effective removal techniques. Conventional wastewater treatment processes are inadequate for removing persistent organic pollutants. Recent studies have increasingly demonstrated that metal-organic frameworks (MOFs) are capable of removing PFASs from water through adsorption techniques. However, there is still constructive discussion on the potential of MOFs in adsorbing and removing PFASs for large-scale engineering applications. This review systematically investigates the use of MOFs as adsorbents for the removal of PFAS in water treatment. This primarily involved a comprehensive analysis of existing literature to understand the adsorption mechanisms of MOFs and to identify factors that enhance their efficiency in removing PFASs. We also explore the critical aspects of regeneration and stability of MOFs, assessing their reusability and long-term performance, which are essential for large-scale water treatment applications. Finally, our study highlights the challenges of removing PFASs using MOFs. Especially, the efficient removal of short-chain PFASs with hydrophilicity is a major challenge, while medium- to long-chain PFASs are frequently susceptible to being captured from water by MOFs through multiple synergistic effects. The ion-exchange force may be the key to solving this difficulty, but its susceptibility to ion interference in water needs to be addressed in practical applications. We hope that this review can provide valuable insights into the effective removal and adsorption mechanisms of PFASs as well as advance the sustainable utilization of MOFs in the field of water treatment, thereby presenting a novel perspective.

Per- and poly-fluoroalkyl substances removal in multi-barrier advanced water purification system for indirect potable reuse.

The study evaluated the removal efficacy of per- and poly-fluoroalkyl substances (PFAS) across various advanced water treatment (AWT) processes in a field-scale AWT train using secondary effluent samples from a full-scale water reclamation facility (WRF). Samples collected from April to October 2020 revealed PFCAs as the dominant PFAS compounds in the WRF secondary effluent, with PFPeA having the highest average concentration and PFSAs in notably lower amounts. Temporal fluctuations in total PFAS concentrations peaked in September 2020, which may reflect the seasonality in PFAS discharges related to applications like AFFFs and pesticides. In assessing AWT processes, coagulation-flocculation-clarification-filtration system showed no notable PFAS reduction, while ozonation resulted in elevated PFBS and PFBA concentrations. Biological activated carbon (BAC) filtration effectively removed long-chain PFAS like PFOS and PFHxS but saw increased concentrations of short-chain PFAS post-treatment. Granular activated carbon (GAC) filtration was the most effective treatment, reducing all PFSAs below the detection limits and significantly decreasing most PFCAs, though short-chain PFCAs persisted. UV treatment did not remove short-chain PFCAs such as PFBA, PFPeA, and PFHxA. The findings highlight the efficacy of AWT processes like GAC in PFAS reduction for potable reuse, but also underscore the challenge presented by short-chain PFAS, emphasizing the need for tailored treatment strategies. PRACTITIONER POINTS: Secondary effluents showed higher concentrations of PFCAs compared to PFSAs. Advanced water treatment effectively removes long-chain PFAS but not short-chain. Ozonation may contribute to formation of short-chain PFAS. BAC is less effective on short-chain PFAS, requiring further GAC treatment.

An investigation of 3M Cordova, IL production worker's per- and polyfluoroalkyl substances biomonitoring results and mortality experience

Per- and polyfluoroalkyl substances (PFAS) are a wide-ranging group of chemicals that have been used in a variety of polymer and surfactant applications. While 3M Cordova, Illinois was not one of 3M's primary manufacturing facilities for the legacy long-chain PFAS (PFOS, PFOA, PFHxS), it has been a major manufacturing site for short-chain PFAS (compounds that are or may degrade to PFBS or PFBA). The purpose of this research focused on: 1) an analysis of biomonitoring data of employees and retirees, and 2) an analysis of the cohort mortality of workers from 1970 to 2018. Employees had higher PFBS and PFBA serum concentrations than the retirees, while retirees had higher concentrations for PFOS, PFOA, and PFHxS. Compared to the 2017–2018 NHANES data, employees’ PFOS and PFHxS concentrations in 2022 were two-fold higher, with PFOA levels comparable. These NHANES data did not include serum PFBS or PFBA. Cross-sectional trends of PFOS and PFOA levels from 1997 to 2022 showed PFOS declined from 151 ng/mL to 10.4 ng/mL. Similarly, PFOA decreased from 100 ng/mL to 1.5 ng/mL. A longitudinal analysis of 48 participants with measurements in both 2006 and 2022 showed concentrations decreased by 74% for PFOS and 90% for PFOA. In the mortality study, 1707 employees who worked 1 day or longer were followed for an average of 25.6 years and had 143 (8%) deaths. There were no significantly elevated risks for any specific cause of death, regardless of latency period (0 or 15 years). While no specific PFAS exposures were examined, worker mortality experience (1970–2018) was analyzed by major departments representing primary work areas. Employees and retirees at the Cordova facility continue to have elevated PFOS and PFHxS serum concentrations compared to the general population, however, their legacy PFAS concentrations have declined over time, consistent with the estimated serum elimination half-lives of these PFAS in humans assuming nominal ambient exposures. For PFBS and PFBA, the results indicated no long-term accumulation in the blood likely due to their short serum elimination half-lives. After nearly 50 years of follow-up, this Cordova workforce showed no increased risk of mortality from cancer or any other specific cause of death.