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Certain PFAS, such as 4:2 fluorotelomer sulfonate, eluted faster from high pH, high sodium columns compared to neutral columns packed with field-collected soil. Other PFAS had more mass eluted from the high pH, high sodium columns.

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

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 (Kex) 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.

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, with90% 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

Rapid small-scale column tests (RSSCTs) are often employed in laboratory testing to determine contaminant treatment effectiveness by anion-exchange resins (AERs) or granular activated carbons (GACs...

Ultraviolet photochemical reaction of sulfite (SO32–) photosensitizer generates strongly reducing hydrated electrons (eaq–; NHE = −2.9 V) that have been shown to effectively degrade individual per-...

Bench-scale experiments were performed to evaluate the electrochemical oxidation, via direct anodic oxidation and indirect oxidation from salt-derived species, of diluted aqueous film forming foam (AFFF) in brine solutions to mimic anion exchange resin regenerant solutions that are loaded with poly- and perfluoroalkyl substances (PFASs). Results showed that initial transformations of the polyfluorinated compounds, which accounted for approximately 45% of the organic fluorine in the initial mixtures, occurred primarily via an indirect oxidation pathway that targeted the non-fluorinated head groups. Depending on the brine solution, this indirect oxidation likely occurred via hydroxyl radical production or salt-derived oxidants (e.g., SO4˙− derived from anodic oxidation of sulfate). However, perfluoroalkyl acid (PFAA) transformation and the overall rate of defluorination were controlled via a combination of direct and indirect electron transfer. Chloride levels (>0.2% by weight) and the presence of 100 mM of the radical scavenger tert-butyl alcohol substantially reduced pseudo first order defluorination rate constants by up to 80%. Evaluation of fluorine mass balances (via fluoride generation and PFAS levels) suggested that up to approximately 41% (based on a fluorine mass balance) electrochemically transformed intermediate products were not identified under some conditions. Thus, evaluating electrochemical treatment effectiveness solely on the disappearance of PFAAs and other suspect analytes described in current analytical libraries could substantially underestimate the PFAS mass remaining in AFFF-impacted waters.

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.

Bench-scale experiments were performed to evaluate poly- and perfluoroalkyl substance (PFAS) desorption from vadose zone soils collected at a site historically impacted with aqueous film-fo...

Per- and polyfluoroalkyl substances (PFASs) are highly mobile in the saturated subsurface, yet aqueous film-forming foam (AFFF)-impacted source zones appear to be long lasting PFAS reservoirs. This study examined the release of over one hundred anionic and zwitterionic PFASs from two AFFF-impacted surface soils under saturated conditions with packed soil columns. Perfluoroalkyl acids (PFAAs) were released more rapidly than their polyfluorinated precursors, while anionic PFASs that were present in partially uncharged states were released more slowly than PFASs that were present entirely as anions, as were zwitterionic PFASs with terminal cationic functional groups when compared with analogous zwitterions with only anionic terminal groups. Nonideal transport was observed in both per- and polyfluorinated classes, as soil column effluent concentrations of slowly released PFASs increased by up to 107-fold with sustained artificial groundwater flow. A flow-interruption experiment suggested the influence of rate-limited desorption on diverse PFAS classes, including PFAAs with as few as four perfluorinated carbons. These results suggest that during infiltration the slow, rate-limited desorption of anionic and zwitterionic PFAA precursors may result in these compounds comprising an increasingly large fraction of the remaining PFASs in AFFF-impacted surface soils.

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

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.

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 (

Bench-scale column experiments were performed to evaluate the applicability of employing rapid small-scale column tests (RSSCTs) for the removal of perfluoroalkyl acids (PFAAs) from groundwater, us...

Bench-scale experiments were performed to measure and evaluate the desorption kinetics of poly- and perfluoroalkyl substances (PFAS) from a vadose zone soil exposed decades ago to aqueous f...

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 (eaq−) 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 C C bond. This approach provides an alternative for treating concentrated PFAS solutions under ambient conditions.

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.

Laboratory batch experiments were performed to assess the reduction of trichloroethene (TCE) and oxygen via natural ferrous minerals. TCE reduction under anoxic conditions was measured via the generation of reduced gases, while oxygen reduction via the generation of hydroxyl radicals was measured as a surrogate for potential TCE oxidation. Results showed that TCE reduction under anoxic conditions was observed for ankerite, siderite, and illite, but not for biotite; acetylene was the primary identified dechlorination product. With the exception of biotite, first-order dechlorination rate constants increased with increasing ferrous content of the mineral, with rate constants ranging from 3.1 × 10−8 to 4.8 10−7 L g−1 d−1. Measured reduction potentials (mV vs SHE) ranged from −104 for illite to +84 for biotite. When normalizing measured first-order dechlorination rate constants to the estimated ferrous iron mineral specific surface area (where surface area was based on nitrogen adsorption analysis of the minerals), TCE dechlorination rate constants increased with increasing reduction potentials. Under oxic conditions, hydroxyl radicals were generated with each of the four minerals. However, mineral activity showed no readily apparent correlation to ferrous content or mineral surface area. In terms of TCE and oxygen reduced per mole of ferrous iron initially present in each mineral, illite was the most reactive of the four minerals. Together, these results suggest that several ferrous minerals may contribute to abiotic dechlorination in the natural environment, and (at least for TCE reduction under anoxic conditions) measurement of ferrous mineral content and reduction potential may serve as useful tools for estimating TCE first-order abiotic dechlorination rate constants.

Although electrochemical treatment has received increased attention with respect to treating poly- and perfluoroalkyl substances (PFAS), studies assessing treatment longevity for the wide r...

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 su...

Electrochemical (EC) treatment presents a low-energy, water-reuse strategy with potential application to decentralized greywater treatment. This study focused on evaluating the impacts of cell configuration, current density, and cathode material on chemical oxygen demand (COD) removal and disinfection byproduct (DBP) formation in greywater. The formation and/or cathodic removal of active chlorine, perchlorate, haloacetic acids, and trihalomethanes were assessed during EC treatment. DBP formation was proportional to current density in undivided EC cells. Sequential anodic-cathodic treatment in divided EC cells resulted in COD removal in the catholyte and anolyte. The anodic COD removal rate (using a mixed metal-oxide anode) was greater than the cathodic removal rate employing boron-doped diamond (BDD) or graphite cathodes, but anodic and cathodic COD removal was similar when a stainless-steel cathode was used. The overall energy demand required for 50% COD removal was 24% less in the divided cells using the graphite or BDD cathodes (13 W-h L−1) compared to undivided cells (20 W-h L−1). Perchlorate formation was observed in undivided experiments (>50 μg/L), but not detected in divided experiments. While haloacetic acids (HAAs) and trihalomethanes (THMs) were generated anodically; they were removed on the cathode surface in the divided cell. These results suggest that divided configurations provide potential to mitigate DBPs in water reuse applications.

This study investigates structure–reactivity relationships within branched per- and polyfluoroalkyl substances (PFASs) undergoing cobalt-catalyzed reductive defluorination reactions. Experimental results and theoretical calculations reveal correlations among the extent of PFAS defluorination, the local C–F bonding environment, and calculated bond dissociation energies (BDEs). In general, BDEs increase in the following order: tertiary C–F bonds < secondary C–F bonds < primary C–F bonds. A tertiary C–F bond adjacent to three fluorinated carbons (or two fluorinated carbons and one carboxyl group) has a relatively low BDE that permits an initial defluorination to occur. Both a biogenic cobalt–corrin complex (B12) and an artificial cobalt–porphyrin complex (Co-PP) are found to catalytically defluorinate multiple C–F bonds in selected PFASs. In general, Co-PP exhibits an initial rate of defluorination that is higher than that of B12. Neither complex induced significant defluorination in linear perfluorooctanoic...

An in situ field demonstration was performed in fractured rock impacted with trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) to assess the impacts of contaminant rebound after removing dissolved contaminants within hydraulically conductive fractures. Using a bedrock well pair spaced 2.4m apart, TCE and DCE were first flushed with water to create a decrease in dissolved contaminant concentrations. While hydraulically isolating the well pair from upgradient contaminant impacts, contaminant rebound then was observed between the well pair over 151days. The magnitude, but not trend, of TCE rebound was reasonably described by a matrix back-diffusion screening model that employed an effective diffusion coefficient and first-order abiotic TCE dechlorination rate constant that was based on bench-scale testing. Furthermore, a shift in the TCE:DCE ratio and carbon isotopic enrichment was observed during the rebound, suggesting that both biotic and abiotic dechlorination were occurring within the rock matrix. The isotopic data and back-diffusion model together served as a convincing argument that matrix back-diffusion was the mechanism responsible for the observed contaminant rebound. Results of this field demonstration highlight the importance and applicability of rock matrix parameters determined at the bench-scale, and suggest that carbon isotopic enrichment can be used as a line of evidence for abiotic dechlorination within rock matrices.

Previous laboratory scale studies indicate nanofiltration (NF) and UV-sulfite photochemical treatments as promising technologies for the removal and destruction, respectively, of per- and polyfluoroalkyl substances (PFASs) from contaminated water. This study reports on a field demonstration of a pilot-scale hybrid NF and UV-sulfite treatment train for the remediation of 12 PFASs detected in groundwater impacted by aqueous film-forming foam (AFFF) at a U.S. Department of Defense installation. For most of the detected PFASs, NF rejection was consistently ≥ 95% over a 30-day field trial when operating at 90% total permeate recovery. Rejection of short-chain perfluorosulfonic acids (PFSAs) by NF decreased when recoveries increased from 90 to 97%; tests with a reverse osmosis (RO) membrane showed ≥ 99% rejection of all PFASs regardless of increasing recovery. UV treatment of the NF reject following 90% permeate recovery resulted in variable destruction of individual PFASs, with rates also being dependent on pH and the identity and concentration of UV photosensitizer. Rates of perfluorocarboxylic acid (PFCA) degradation were greater than those measured for PFSAs and perfluoroalkyl acid (PFAA) precursors and were independent of perfluoroalkyl chain length. In contrast, rates of PFSA degradation increased with increasing chain length. Consistent levels of PFAS degradation by UV-sulfite were observed during a 30-day demonstration experiment in NF reject water amended with 10 mM sulfite and adjusted to pH 11.2. Collectively, > 75% of the detected PFAS mass in the NF reject was destroyed after 4 h of UV treatment, increasing to > 90% after 8 h of treatment. An analysis of electrical energy inputs for the hybrid NF/UV-sulfite treatment train showed energy per order magnitude (EE/O) requirements ranging from ≤ 13.1 kWh/m3 for PFCAs and 14.1 kWh/m3 for PFOS to values > 100 kWh/m3 for more recalcitrant short-chain PFSA analogues. The UV reactor and water-cooling system were the major contributors to overall energy requirements and represent the greatest opportunities for improving efficiency of the technology.

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.

Per- and polyfluoroalkyl substances (PFASs) are a heterogeneous group of persistent organic pollutants that have been detected in various environmental compartments around the globe. Emerging research has revealed the preferential accumulation of PFASs in shallow soil horizons, particularly at sites impacted by firefighting activities, agricultural applications, and atmospheric deposition. Once in the vadose zone, PFASs can sorb to soil, accumulate at interfaces, become volatilized, be taken up in biota, or leach to the underlying aquifer. At the same time, polyfluorinated precursor species may transform into highly recalcitrant perfluoroalkyl acids, changing their chemical identity and thus transport behavior along the way. In this review, we critically discuss the current state of the knowledge and aim to interconnect the complex processes that control the fate and transport of PFASs in the vadose zone. Furthermore, we identify key challenges and future research needs. Consequently, this review may serve as an interdisciplinary guide for the risk assessment and management of PFAS-contaminated sites.

Laboratory batch experiments were performed to assess the impacts of temperature and mineralogy on the abiotic dechlorination of tetrachloroethene (PCE) or trichloroethene (TCE) due to the presence of ferrous minerals in natural aquifer clayey soils under anaerobic conditions. A combination of x-ray diffraction (XRD), magnetic susceptibility, and ferrous mineral content were used to characterize each of the 3 natural soils tested in this study, and dechlorination at temperatures ranging from 20 to 55°C were examined. Results showed that abiotic dechlorination occurred in all 3 soils examined, yielding reduced gas abiotic dechlorination products acetylene, butane, ethene, and/or propane. Bulk first-order dechlorination rate constants (kbulk), scaled to the soil:water ratio expected for in situ conditions, ranged from 2.0×10-5day-1 at 20°C, to 32×10-5day-1 at 55°C in the soil with the greatest ferrous mineral content. For the generation of acetylene and ethene from PCE, the reaction was well described by Arrhenius kinetics, with an activation energy of 91kJ/mol. For the generation of coupling products butane and propane, the Arrhenius equation did not provide a satisfactory description of the data, likely owing to the complex reaction mechanisms associated with these products and/or diffusional mass transfer processes associated with the ferrous minerals likely responsible for these coupling reactions. Although the data set was too limited to determine a definitive correlation, the two soils with elevated ferrous mineral contents had elevated abiotic dechlorination rate constants, while the one soil with a low ferrous mineral content had a relatively low abiotic dechlorination rate constant. Overall, results suggest intrinsic abiotic dechlorination rates may be an important long-term natural attenuation component in site conceptual models for clays that have the appropriate iron mineralogy.