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Per- and polyfluoroalkyl substances (PFAS) are persistent and bioaccumulative contaminants that are widely used in industrial applications and consumer products and pose significant risks to ecosystems and human health. Acidimicrobium sp. Strain A6 (A6), which is common in acidic, and iron rich soils and sediments is capable of both anaerobic ammonium (NH 4 + ) oxidation under iron reduction (Feammox) and defluorination of perfluorinated alkyl substances, such as perfluoroalkyl acids (PFAAs). This study investigates the potential for biostimulating A6 via the supply of NH 4 + and ferric iron (Fe(III)) with the goal of defluorinating PFAAs. Sediment samples from acidic, iron-rich, AFFF (aqueous film forming foam) impacted sites were collected and incubated with added Fe(III) and NH 4 + . Quantitative PCR was used to track A6 numbers as well as dehalogenase and F - ion transporter genes during these incubations; changes in the microbial community structure were tracked through 16S rRNA gene sequencing. The findings reveal that the addition of Fe(III) and NH 4 + stimulated the Feammox reaction and A6 growth and enhanced the degradation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Results also show a significant presence and activity of the above-mentioned genes in these incubations. The insights gained from this study could inform bioremediation strategies for PFAS-contaminated environments, especially in geochemical settings that favor the presence of A6., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Peter Jaffe reports financial support was provided by US Department of Defense. Peter Jaffe has patent #“Biodegradation of Fluorochemicals,” U.S. Provisional Application No. 62/792,971, January 16, 2019, (with S. Huang). pending to Princeton University. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Some Per- and polyfluoroalkyl substances (PFAS) are strongly retained in the vadose zone due to their sorption to both soils and air-water interfaces. While significant research has been dedicated to understanding equilibrium behavior for these multi-phase retention processes, leaching and desorption from aqueous film-forming foam (AFFF) impacted soils under field relevant conditions can exhibit significant deviations from equilibrium. Herein, laboratory column studies using field collected AFFF-impacted soils were employed to examine the leaching of perfluoroalkyl acids (PFAAs) under simulated rainfall conditions. The HYDRUS 1-D model was calibrated to estimate the unsaturated hydraulic properties of the soil in a layered system using multiple boundary condtions. Forward simulations of equilibrium PFAS partitioning using the HYDRUS model and simplified mass balance calculations showed good agreement with the net PFAS mass flux out of the column. However, neither were able to predict the PFAS concentrations in the leached porewater. To better understand the mechanisms controlling the leaching behavior, the HYDRUS 1-D two-site leaching model incorporating solid phase rate limitation and equilibrium air-water interfacial partitioning was employed. Three variations of the novel model incorporating different forms of equilibrium air-water interfacial partitioning were considered using built-in numerical inversion. Results of numerical inversion show that a combination of air-water interfacial collapse and rate-limited desorption from soils can better predict the unique leaching behavior exhibited by PFAAs in AFFF-impacted soils. A sensitivity analysis of the initial conditions and rate-limited desorption terms was conducted to assess the agreement of the model with measured data. The models demonstrated herein show that, under some circumstances, laboratory equilibrium partitioning data can provide a reasonable estimation of total mass leaching, but fail to account for the significant rate-limited, non-Fickian transport which affect PFAA leaching to groundwater in unsaturated soils., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: John Forrest Stults reports financial support was provided by Strategic Environmental Research and Development Program. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Poly- and perfluoroalkyl substance (PFAS) leaching from unsaturated soils impacted with aqueous film-forming foams (AFFFs) is an environmental challenge that remains difficult to measure and predict. Complicating measurements and predictions of this process is a lack of understanding between the PFAS concentrations measured in a collected environmental unsaturated soil sample, and the PFAS concentrations measured in the corresponding porewater using field-deployed lysimeters. The applicability of bench-scale batch testing to assess this relationship also remains uncertain. In this study, field-deployed porous cup suction lysimeters were used to measure PFAS porewater concentrations in unsaturated soils at 5 AFFF-impacted sites. Field-measured PFAS porewater concentrations were compared to those measured in porewater extracted in the laboratory from collected unsaturated soil cores, and from PFAS concentrations measured in the laboratory using batch soil slurries. Results showed that, despite several years since the last AFFF release at most of the test sites, precursors were abundant in 3 out of the 5 sites. Comparison of field lysimeter results to laboratory testing suggested that the local equilibrium assumption was valid for at least 3 of the sites and conditions of this study. Surprisingly, PFAS accumulation at the air-water interface was orders of magnitude less than expected at two of the test sites, suggesting potential gaps in the understanding of PFAS accumulation at the air-water interface at AFFF-impacted sites. Finally, results herein suggest that bench-scale testing on unsaturated soils can in some cases be used to inform on PFAS in situ porewater concentrations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Both quantifiable and semi-quantifiable poly- and perfluoroalkyl substances (PFAS) were evaluated in the influent, effluent, and biosolids of 38 wastewater treatment plants. PFAS were detected in all streams at all facilities. For the means of the sums of detected, quantifiable PFAS concentrations were 98 ± 28 ng/L, 80 ± 24 ng/L, and 160,000 ± 46,000 ng/kg (dry weight basis) in the influent, effluent, and biosolids (respectively). In the aqueous influent and effluent streams this quantifiable PFAS mass was typically associated with perfluoroalkyl acids (PFAAs). In contrast, quantifiable PFAS in the biosolids were primarily polyfluoroalkyl substances that potentially serve as precursors to the more recalcitrant PFAAs. Results of the total oxidizable precursor (TOP) assay on select influent and effluent samples showed that semi-quantified (or, unidentified) precursors accounted for a substantial portion (21 to 88%) of the fluorine mass compared to that associated with quantified PFAS, and that this fluorine precursor mass was not appreciably transformed to perfluoroalkyl acids within the WWTPs, as influent and effluent precursor concentrations via the TOP assay were statistically identical. Evaluation of semi-quantified PFAS, consistent with results of the TOP assay, showed the presence of several classes of precursors in the influent, effluent, and biosolids; perfluorophosphonic acids (PFPAs) and fluorotelomer phosphate diesters (di-PAPs) occurred in 100 and 92% of biosolid samples, respectively. Analysis of mass flows showed that, for both quantified (on a fluorine mass basis) and semi-quantified PFAS, the majority of PFAS exited WWTPs through the aqueous effluent compared to the biosolids stream. Overall, these results highlight the importance of semi-quantified PFAS precursors in WWTPs, and the need to further understand the impacts of their ultimate fate in the environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Air-water interfacial retention of poly- and perfluoroalkyl substances (PFASs) is increasingly recognized as an important environmental process. Herein, column transport experiments were used to measure air-water interfacial partitioning values for several perfluoroalkyl ethers and for PFASs derived from aqueous film-forming foam, while batch experiments were used to determine equilibrium K ia data for compounds exhibiting evidence of rate-limited partitioning. Experimental results suggest a Freundlich isotherm best describes PFAS air-water partitioning at environmentally relevant concentrations (10 1 -10 6 ng/L). A multiparameter regression analysis for K ia prediction was performed for the 15 PFASs for which equilibrium K value of 0.65 and validated across a range of relevant concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and hexafluoropropylene oxide-dimer acid (i.e., GenX). A mass action model was further modified to account for the changing ionic strength on PFAS air-water interfacial sorption. The final result was two distinct QSPRs for estimating PFAS air-water interfacial partitioning across a range of aqueous concentrations and ionic strengths.ia values were determined, assessing 246 possible combinations of 8 physicochemical and system properties. Quantitative structure-property relationships (QSPRs) based on three to four parameters provided predictions of high accuracy without model overparameterization. Two QSPRs ( R 2 values of 0.92 and 0.83) were developed using an assumed average Freundlich n value of 0.65 and validated across a range of relevant concentrations for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and hexafluoropropylene oxide-dimer acid (i.e., GenX). A mass action model was further modified to account for the changing ionic strength on PFAS air-water interfacial sorption. The final result was two distinct QSPRs for estimating PFAS air-water interfacial partitioning across a range of aqueous concentrations and ionic strengths.

Per- and polyfluoroalkyl substances (PFASs) are frequently found at high concentrations in the subsurface of aqueous film forming foam (AFFF)-impacted sites. Geochemical parameters affect the release of PFASs from source area soils into groundwater but have not been extensively studied for soils that have been historically impacted with AFFF. This study investigated the effects of pH and salt concentrations on release of anionic and zwitterionic PFASs from AFFF-impacted soils in flow-through saturated columns. High pH (10) columns with elevated sodium concentrations had higher cumulative masses eluted of several PFASs compared to pH 3 and pH 7 columns with lower sodium concentrations, likely caused by changes to soil organic matter surface charge. Four PFASs ( e.g. 4:2 fluorotelomer sulfonate, perfluorobutane sulfonamido acetic acid) eluted significantly earlier in both pH 3 and pH 10/high NaCl columns compared to pH 7 columns. The results of this study suggest that shifts in pH for soils located at AFFF-impacted sites - particularly raising the pH - may mobilize sorbed PFASs, specifically longer-chain and zwitterionic compounds that are typically strongly sorbed to soil.

While several studies have focused on perfluoroalkyl acid (PFAA) leaching from soils, field studies evaluating the relationship between PFAA mass removal and porewater concentrations as the PFAA source becomes depleted are lacking. Herein, in situ water flushing was performed at a site historically impacted with AFFF to accelerate the leaching of PFAAs from unsaturated soils in a highly characterized field test cell. Porous cup suction lysimeters were used to assess the changes in PFAA porewater concentrations as a function of PFAA mass removal from the unsaturated soils, where flushing was intermittently paused to determine ambient PFAA porewater concentrations. Results showed that the fractional decreases in PFAA porewater concentrations during flushing exceeded the fractional decrease in PFAA mass removal from the soil. PFOS porewater concentrations decrease by 76% (with negligible rebound) compared to only a 7.4% decrease in overall PFOS mass removed from the unsaturated zone. Overall, the results observed herein suggest that, when considering soil impacts to groundwater, less stringent soil cleanup criteria than those that consider an equivalent relationship between mass removal and mass discharge may be appropriate. In addition, remedial approaches that remove only a modest fraction of the PFAA soil mass may be protective of underlying groundwater, particularly for perfluorinated sulfonates with at least six carbons.

UV-sulfite has been shown to effectively degrade per- and polyfluoroalkyl substances (PFASs) in single-solute experiments. We recently reported treatment of 15 PFASs, including perfluoroalkyl sulfonic acids (PFSAs), perfluoroalkyl carboxylic acids (PFCAs), and fluorotelomer sulfonic acids (FTSs), detected in aqueous film-forming foam (AFFF) using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Here, we extend the analysis within those original reaction solutions to include the wider set of PFASs in AFFF for which reactivity is largely unknown by applying recently established LC-QTOF-MS suspect screening and semiquantitative analysis protocols. Sixty-eight additional PFASs were detected (15 targeted + 68 suspect screening = 83 PFASs) with semiquantitative analysis, and their behavior was binned on the basis of (1) detection in untreated AFFF, (2) PFAS photogeneration, and (3) reactivity. These 68 structures account for an additional 20% of the total fluorine content in the AFFF (targeted + suspect screening = 57% of total fluorine content). Structure-reactivity trends were also revealed. During treatment, transformations of highly reactive structures containing sulfonamide (-SO 2 N-) and reduced sulfur groups (e.g., -S- and -SO-) adjacent to the perfluoroalkyl [F(CF 2 ) n -] or fluorotelomer [F(CF 2 ) n (CH 2 ) 2 -] chain are likely sources of PFCA, PFSA, and FTS generation previously reported during the early stages of reactions. The results also show the character of headgroup moieties adjacent to the F(CF 2 ) n -/F(CF 2 ) n (CH 2 ) 2 - chain (e.g., sulfur oxidation state, sulfonamide type, and carboxylic acids) and substitution along the F(CF 2 ) n - chain (e.g., H-, ketone, and ether) together may determine chain length-dependent reactivity trends. The results highlight the importance of monitoring PFASs outside conventional targeted analytical methodologies.

Bench-scale experiments were performed to interrogate poly- and perfluoroalkyl substance (PFAS) enrichment in the water surface microlayer (SML). In initial experiments using electrolyte-only solutions, the perfluorooctane sulfonate (PFOS) and perfluorooctane carboxylate (PFOA) enrichment in the SML were reasonably (with a factor of 2) described by the Gibbs adsorption equation coupled with a Freundlich-based interfacial adsorption model. Enrichment in the SML among perfluorinated sulfonates and perfluorinated carboxylates of varying chain lengths was proportional to their surface activity. The PFOS enrichment factor (EF), defined as the PFAS concentration in the SML divided by the concentration in the bulk water, was 18 in a 200 mg/l NaCl solution. The presence of elevated organic carbon levels in synthetic surface waters inhibited PFAS accumulation in the SML, with resulting EF values of approximately 1 for all PFAS. However, in the presence of elevated organic levels coupled with foam, PFAS enrichment in the foam was observed, with a foam EF of 25 measured for PFOS in synthetic surface waters. PFAS EF values measured in several natural surface waters without foam showed little variation among the waters tested, with PFOS EF values ranging between 6 and 10. Together, these results suggest that PFAS accumulation in the SML is largely controlled by PFAS sorption at the air-water interface for the conditions examined in this study, and the presence of foam with natural organics enhances PFAS uptake at the water surface., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Jennifer Field reports financial support was provided by Strategic Environmental Research and Development Program., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This study reports the results of an 8-month pilot study comparing both regenerable and emerging single-use anion exchange resins (AERs) for treatment of per- and polyfluoroalkyl substances (PFASs) at a source zone impacted by historical use of aqueous film-forming foam (AFFF). Two regenerable (Purolite A860 and A520E) and three single-use (Purolite PFA694E, Calgon CalRes 2301, and Dowex PSR2+) AERs were tested in parallel, collecting effluent samples after treatment for 30-sec and 2-min total empty bed contact time (EBCT). Results demonstrate that single-use AERs significantly outperform regenerable resins, particularly for treatment of long-chain perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs). No detectable concentrations of ≥C7 PFCAs or PFSAs were observed within 150,000 bed volumes (BVs) after treatment with the single-use resins (2-min EBCT). Analysis of effluent samples following 30-sec EBCT treatment shows that even the shortest-chain PFSAs do not reach 50% breakthrough within the first 350,000 BVs, though differences in removal of short-chain PFCAs was less dramatic. The regenerable polyacrylic A860 resin performed very poorly compared to all polystyrene resins, with >90% breakthrough of all PFASs occurring within 10,000 BVs. The greater affinity of polystyrene resins is attributed to increased hydrophobic interactions in addition to electrostatic ion exchange. Analysis of breakthrough profiles reveals empirical correlation with ion exchange affinity coefficients (logK ex ) measured in batch experiments. Postmortem analysis of PFASs extracted from spent resins revealed chromatographic elution behavior and competition among PFASs for adsorption to the resins. PFSAs and long-chain PFCAs were preferentially adsorbed to earlier sections in the AER columns, whereas short-chain PFCAs were competitively displaced towards the later sections of the columns and into the effluent, consistent with effluent concentrations of the latter structures exceeding influent values. These results provide insights into the mechanisms that govern PFAS adsorption to AERs in real multisolute groundwater matrices and support findings from other diverse sites regarding PFAS affinity, elution behavior, and competition for exchange sites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

Predicting the transport of perfluoroalkyl acids (PFAAs) in the vadose zone is critically important for PFAA site cleanup and risk mitigation. PFAAs exhibit several unusual and poorly understood transport behaviors, including partitioning to the air-water interface, which is currently the subject of debate. This study develops a novel use of quasi-saturated (residual air saturation) column experiments to estimate chemical partitioning parameters of both linear and branched perfluorooctane sulfonate (PFOS) in unsaturated soils. The ratio of linear-to-branched air-water interfacial partitioning constants for all six experiments was 1.62 ± 0.24, indicating significantly greater partitioning of linear PFOS isomers at the air-water interface. Standard breakthrough curve analysis and numerical inversion of HYDRUS models support the application of a Freundlich isotherm for PFOS air-water interfacial partitioning below a critical reference concentration (CRC). Data from this study and previously reported unsaturated column data on perfluorooctanoate (PFOA) were reevaluated to examine unsaturated systems for transport nonidealities. This reanalysis suggests both transport nonidealities and Freundlich isotherm behavior for PFOA below the CRC using drainage-based column methods, contrary to the assertions of the original authors. Finally, a combined Freundlich-Langmuir isotherm was proposed to describe PFAA air-water interfacial partitioning across the full range of relevant PFAA concentrations.

Finished biosolids were collected and characterized from seven municipal water resource recovery facilities. Poly- and perfluoroalkyl substances (PFAS) for the 54 quantified in the biosolids ranged from 323 ± 14.1 to 1100 ± 43.8 µg/kg (dry weight basis). For all biosolids, greater than 75% of the PFAS fluorine mass was associated with precursors. Di-substituted polyfluorinated phosphate esters (diPAPs) were the most abundant PFAS identified in the biosolids. The total oxidizable precursor assay on biosolids extracts generally failed to quantify the amount of precursors present, in large part due to the fact that diPAPS were not fully transformed during the TOP assay. Outdoor biosolids column leaching experiments intended to simulate biosolids land application showed sustained PFAS leaching over the 6-month study duration. Perfluoroalkyl acid (PFAA) concentrations in leachate, when detected, typically ranged in the 10 s to 100 s of ng/L; no diPAPs were detected in the leachate. The PFAA leaching from the biosolids exceeded the PFAA mass initially present in the biosolids (typically by greater than an order of magnitude), but the cumulative PFAA mass leached did not exceed the molar equivalents that could be explained by transformation of quantified precursors. These results highlight the importance of PFAA precursors initially present in biosolids and their contribution to long term leaching of PFAAs from land-applied biosolids., (Copyright © 2022. Published by Elsevier Ltd.)

Field-deployed lysimeters were used to measure the concentrations of poly- and perfluoroalkyl substances (PFASs) in soil porewater at a site historically impacted with aqueous film forming foam (AFFF). Samples collected over a 49-day period showed that perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) were the PFASs with the highest concentrations in porewater, with concentrations of approximately 10,000 and 25,000 ng L -1 , respectively. The corresponding average mass flux to underlying groundwater observed for PFOS and PFHxS was 28,000 ± 11,000 and 92,000 ± 32,000 ng m -2 d -1 , respectively. Employing the use of batch desorption isotherms (soil:water slurries) to determine desorption K d values resulted in an overestimation of PFAS porewater concentrations by a factor for 1.4 to 4. However, using the desorption K d values from the batch desorption isotherms in combination with a PFAS mass balance that incorporated PFAS sorption at the air-water interface resulted in improved predictions of the PFAS porewater concentrations. This improvement was most notable for PFOS, where inclusion of air-water interfacial sorption resulted in a 58% reduction in the predicted PFOS porewater concentration and predicted PFOS porewater concentrations that were identical (within the 95% confidence interval) to the lysimeter measured PFOS porewater concentration. Overall these results highlight the potentially important role of air-water interfacial sorption on PFAS migration in AFFF-impacted unsaturated soils in an in situ field setting., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Poly- and perfluorinated alkyl substances (PFASs) frequently co-occur with fuel-derived contaminants because of the use of aqueous film-forming foam (AFFF). Biosparging is a common remediation technology that injects oxygen into the saturated zone to encourage aerobic biodegradation, thereby altering aquifer redox conditions and potentially facilitating the biotransformation of polyfluorinated substances. Between 136 and 280 pore volumes of nitrogen-sparged or oxygen-sparged artificial groundwater amended with toluene were pumped through four saturated, AFFF-impacted soil columns to assess impacts on PFAS release and transformation. Column effluents and soils were analyzed for PFASs by high-resolution mass spectrometry. Significantly higher concentrations of five PFASs eluted from O 2 -sparged columns compared to N 2 -sparged columns shortly after sparging was initiated. The mass fractions eluted of many zwitterionic, sulfonamide-based PFASs were higher in both sets of columns than unaltered, non-biostimulated columns. Mass balance calculations suggested the transformation of sulfonamide-based precursors to perfluorinated sulfonamides (i.e., perfluorohexanesulfonamide) in oxygen- and nitrogen-sparged columns: recoveries of perfluorinated sulfonamides were 158-235% for C3-C6 homologs but recoveries of several prominent sulfonamide-based zwitterions were low. For example, the recovery of n -carboxyethyldimethyl-ammoniopropyl perfluorohexanesulfonamide was 9-13%. These results suggest biosparging can enhance the transformation and release of PFASs in saturated soils, which has important implications for site characterization and remediation.

Although anion exchange resin (AER) treatment is considered an effective technology for removing per- and polyfluoroalkyl substances (PFASs) from impacted water, the environmental impacts associated with AER regeneration have not been systematically explored. In particular, the trade-offs of altering the composition of the regeneration solution and disposing of or recycling the waste regeneration solution are not known. To fill these important gaps in the literature, this research conducted a comparative life cycle assessment (LCA) of an AER-based PFAS remediation system with different regeneration scenarios including disposing of waste regeneration solution via incineration, reusing the organic cosolvent and brine fractions of the waste regeneration solution, and altering the composition of the regeneration solution to avoid organic cosolvent or NaCl. The results show that disposing of waste regeneration solution via incineration, without recycling organic cosolvent or brine, had the greatest environmental impact, and that incineration accounted for the greatest impact among contributing processes. Recycling of the cosolvent (or cosolvent and brine) fraction of the waste regeneration solution resulted in lower environmental impacts due to reduced mass of waste disposed of via incineration. Replacing NaCl in the brine with an alternative salt resulted in higher environmental impacts, with salts derived from chemical production, such as ammonium chloride and potassium carbonate, showing the largest increases in impacts. The results of this research highlight the importance of understanding the fate of PFASs during incineration, and the need for PFAS destruction technologies that can be coupled to AER regeneration to avoid incineration., (Copyright © 2021. Published by Elsevier Ltd.)

Diffusion through a water saturated silty clay soil column was measured for six perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). An aqueous pore diffusion model, which incorporated linear adsorption parameters measured independently in batch tests and a tortuosity factor determined independently using a bromide tracer test, was used to describe the experimental diffusion data. The diffusion model substantially underpredicted PFAA diffusion through the soil column for the more strongly sorbing PFAAs (most notably PFOS). Instead, application of a diffusion model that included a surface diffusion-like process provided substantially improved prediction of PFAA diffusion through the soil. The ratio of the observed pore diffusion coefficient to the observed surface diffusion coefficient ranged from 13 (for perfluorohexane sulfonate) to 0.88 for PFOS. These results suggest that surface diffusion serves a potentially important role for strongly sorbing PFAAs in clay-rich soils, and highlights the need for additional studies into the coupled adsorption and diffusion of PFAAs in low permeability media., (Copyright © 2021. Published by Elsevier B.V.)

A key gap in the literature on the treatment of per- and polyfluoroalkyl substances (PFAS) in impacted water is the absence of a review article dedicated to anion exchange resin (AER) treatment. This gap is important because previous research has consistently shown adsorption by AER to be one of the most effective treatment processes for PFAS removal from impacted water, and AER is one of the most commonly deployed technologies in the field. Given the scope of the previous review articles on PFAS removal by various adsorbent types, the sections on AER do not explore the full depth of PFAS and AER interactions nor cover the breadth of AER testing conditions. Accordingly, the goal of this paper was to critically review the available peer-reviewed literature on PFAS removal from water by AER. The specific objectives of the review were to synthesize the previous literature results on (1) batch adsorption behavior, (2) impact of water chemistry conditions, (3) continuous-flow adsorption, (4) adsorption modeling, (5) regeneration, and (6) weak-base AER. Following from critical review of the literature, the future research priorities discussed include: (i) improving the underlying science that governs PFAS-resin interactions, (ii) improving methods for resin regeneration and management of PFAS-contaminated concentrate streams, and (iii) comparative life cycle environmental and economic analyses for ion exchange treatment systems relative to competing technologies., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Per-and poly-fluoroalkyl substances (PFASs) are a class of persistent compounds that are resistant to degradation. Here we developed an effective method of degrading perfluorooctanesulfonate (PFOS) by hydrated electrons (e aq - ) that are generated from 3-indole-acetic-acid (IAA) upon UV irradiation. The method takes advantage of spatial proximity of IAA and PFOS by their co-sorption to an organic polymer, 12-aminolauric acid (ALA), which was pre-intercalated into the interlayer space of an expandable clay mineral, montmorillonite. The interlayer spacing of this clay nanocomposite is greatly expanded relative to unmodified montmorillonite. The maximum adsorption capacity of IAA and PFOS is 168 and 1550 mmol/kg, respectively. This process achieved 40-70% defluorination of a 10 ppm PFOS solution at neutral pH in a 325 mL vessel. The presence of bicarbonate and chloride ions, or natural groundwater showed a minimal impact on PFOS degradation. Based on identification of prominent degradation products, a degradation pathway is proposed, where the primary degradation process is breakage of the C-F bonds (with fluorine replaced by hydrogen), with some cleavage of the CC bond. This approach provides an alternative for treating concentrated PFAS solutions under ambient conditions., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Despite benefits to the firefighting industry, the release of per- and polyfluoroalkyl substances (PFASs) from aqueous film-forming foam (AFFF) into aquatic systems poses significant risks to human health and other organisms. While anion-exchange technologies have proven to be effective for removing perfluoroalkyl acids (PFAAs) from water, their effectiveness for removing the diverse PFAS structures discovered in AFFF remains unknown. Here, we report on the adsorption of 75 PFASs, including 63 polyfluorinated substances, in a diluted AFFF mixture using 14 commercially available ion-exchange (IX)/nonionic resins and granular activated carbon (GAC). Results showed that anion-exchange resins (AERs) exhibited significant adsorption of PFASs compared to cation-exchange resins (CERs), nonionic resins (NIRs), and GAC regardless of the PFAS's predicted charge. Isotherm data showed that macroporous AERs have a higher PFAS adsorption capacity compared to gel-type AERs. Cross-correlation comparison of PFAS/Cl - selectivity coefficients ( K ex ) for each PFAS-AER combination showed that the hydrophobicity of the AER functional group, and polymer matrix played a dominant role in determining resin affinity for PFASs. PFAS structural characteristics also significantly affected adsorption, with increasing chain length and a net negative charge increasing the extent of adsorption. Results from this study provide guidelines for the selection of resins to adsorb a wider range of PFASs and meaningful insights for the development of quantitative models for IX treatment of AFFF-impacted water.

Ultraviolet photochemical reaction of sulfite (SO 3 ) photosensitizer generates strongly reducing hydrated electrons (e 2- ; NHE = -2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize e aq reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via e - ; NHE = -2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize e aq - reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via e aq - reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.

Bench-scale experiments were performed to assess uptake of poly- and perfluoroalkyl substances (PFAS), both single compounds and mixtures, at the air-water interface. The focus was on evaluating uptake at field-relevant PFAS concentrations (<2 × 10 -4 mol m -3 or 0.1 mg L -1 ), assessing the impacts of various PFAS mixtures, and quantifying the impacts of background NaCl concentrations. Both interfacial tension measurements and direct quantification of PFAS mass sorbed at the air-water interface in water films were used to evaluate PFAS interfacial partitioning. Results showed that a Freundlich-based model, rather than a Langmuir-based model, described perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) interfacial uptake. At lower and field-relevant PFOS and PFOA concentrations, the Langmuir-based model underpredicted interfacial uptake by up to several orders of magnitude. The interfacial partition coefficient, k aw , increased as PFAS concentrations decreased. Results also showed that the interfacial tension and interfacial uptake of PFAS mixtures were (within a factor of 2) predicted based on the single solute systems assuming ideal dilute behavior. Furthermore, the addition of NaCl at concentrations of up to 0.01 M increased PFOS uptake by less than a factor of 2 at field-relevant PFOS concentrations. The results presented herein have important implications for PFAS migration in unsaturated soils as well as for remedial technologies that rely on PFAS interfacial sorption, particularly at field-relevant PFAS concentrations.

While oxidative technologies have been proposed for treatment of waters impacted by aqueous film forming foams (AFFFs), information is lacking regarding the transformation pathways for the chemical precursors to the perfluoroalkyl acids (PFAAs) typically present in such waters. This study examined the oxidative electrochemical treatment of poly- and perfluoroalkyl substances (PFASs) for two AFFF-impacted groundwaters. The bulk pseudo first order rate constant for PFOA removal was 0.23 L h -1 A -1 ; for PFOS, this value ranged from 0.084 to 0.23 L h -1 A -1 . Results from the first groundwater studied suggested a transformation pathway where sulfonamide-based PFASs transformed to primarily perfluorinated sulfonamides and perfluorinated carboxylic acids (PFCAs), with subsequent defluorination of the PFCAs. Transient increases in the perfluorinated sulfonamides and PFCAs were observed. For the second groundwater studied, no transient increases in PFAAs were measured, despite the presence of similarly structured suspected PFAA precursors and substantial defluorination. For both waters, suspected precursors were the primary sources of the generated fluoride. Assessment of precursor compound transformation noted the formation of keto-perfluoroalkanesulfonates only in the second groundwater. These results confirm that oxidation and defluorination of suspected PFAA precursors in the second groundwater underwent transformation via a pathway different than that of the first groundwater, which was not captured by total oxidizable precursor assay.

Laboratory experiments were performed to evaluate the use of electrochemical treatment for the decomposition of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), as well as other perfluoroalkyl acids (PFAAs), in aqueous film forming foam (AFFF)-impacted groundwater collected from a former firefighter training area and PFAA-spiked synthetic groundwater. Using a commercially-produced Ti/RuO2 anode in a divided electrochemical cell, PFOA and PFOS decomposition was evaluated as a function of current density (0-20 mA/cm(2)). Decomposition of both PFOA and PFOS increased with increasing current density, although the decomposition of PFOS did not increase as the current density was increased above 2.5 mA/cm(2). At a current density of 10 mA/cm(2), the first-order rate constants, normalized for current density and treatment volume, for electrochemical treatment of both PFOA and PFOS were 46 × 10(-5) and 70 × 10(-5) [(min(-1)) (mA/cm(2))(-1) (L)], respectively. Defluorination was confirmed for both PFOA and PFOS, with 58% and 98% recovery as fluoride, respectively (based upon the mass of PFOA and PFOS degraded). Treatment of other PFAAs present in the groundwater also was observed, with shorter chain PFAAs generally being more recalcitrant. Results highlight the potential for electrochemical treatment of PFAAs, particularly PFOA and PFOS, in AFFF-impacted groundwater., (Copyright © 2015 Elsevier B.V. All rights reserved.)