Sulfonamide Per- and Polyfluoroalkyl Substances Can Impact Microorganisms Used in Aromatic Hydrocarbon and Trichloroethene Bioremediation.

Per- and polyfluoroalkyl substances (PFASs) from aqueous film forming foams (AFFFs) can hinder bioremediation of co-contaminants such as trichloroethene (TCE) and benzene, toluene, ethylbenzene, and xylene (BTEX). Anaerobic dechlorination can require bioaugmentation of Dehalococcoides, and for BTEX, oxygen is often sparged to stimulate in situ aerobic biodegradation. We tested PFAS inhibition to TCE and BTEX bioremediation by exposing an anaerobic TCE-dechlorinating coculture, an aerobic BTEX-degrading enrichment culture, and an anaerobic toluene-degrading enrichment culture to n-dimethyl perfluorohexane sulfonamido amine (AmPr-FHxSA), perfluorohexane sulfonamide (FHxSA), perfluorohexanesulfonic acid (PFHxS), or nonfluorinated surfactant sodium dodecyl sulfate (SDS). The anaerobic TCE-dechlorinating coculture was resistant to individual PFAS exposures but was inhibited by >1000× diluted AFFF. FHxSA and AmPr-FHxSA inhibited the aerobic BTEX-degrading enrichment. The anaerobic toluene-degrading enrichment was not inhibited by AFFF or individual PFASs. Increases in amino acids in the anaerobic TCE-dechlorinating coculture compared to the control indicated stress response, whereas the BTEX culture exhibited lower concentrations of all amino acids upon exposure to most surfactants (both fluorinated and nonfluorinated) compared to the control. These data suggest the main mechanisms of microbial toxicity are related to interactions with cell membrane synthesis as well as protein stress signaling.

Research Needs Regarding the Vapor Intrusion Potential of Volatile Per- and Polyfluoroalkyl Substances.

Certain per- or polyfluoroalkyl substances [e.g., fluorotelomer alcohols (FtOHs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)] have sufficient volatility to merit investigation of the vapor intrusion pathway on a site-specific basis, when they occur as subsurface contaminants in sufficient concentrations near occupied buildings. This perspective summarizes some of the evidence that these categories of per- or polyfluoroalkyl substances are volatile and offers specific research questions and objectives, for purposes of further assessing whether FtOHs, FOSAs, and/or FOSEs can pose indoor exposures via soil vapor intrusion and under what circumstances.

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.

Repeated Aqueous Film-Forming Foams Applications: Impacts on Polyfluoroalkyl Substances Retention in Saturated Soil.

Historical practices at firefighter-training areas involved repeated aqueous film-forming foams (AFFFs) applications, resulting in source zones characterized by high concentrations of perfluoroalkyl and polyfluoroalkyl substances (PFAS). Repeated applications of AFFF composed of 14 anionic and 23 zwitterionic perfluoroalkyl substances (PFAS) were conducted on a single one-dimensional saturated soil column to quantify PFAS retention. An electrofluorination-based (3M) Milspec AFFF, which was above the mixture's critical micelle concentration (CMC), was at application strength (3%, v/v). Retention and retardation of PFAS mass increased with each successive AFFF addition, although the PFAS concentration profiles for subsequent applications differed from the initial. Greater degree of mass retention and retardation correlated with longer PFAS carbon-fluorine chain length and charged-headgroup type and as a function of AFFF application number. Anionic PFAS were increasingly retained with each subsequent AFFF application, while zwitterionic PFAS exhibited an alternating pattern of sorption and desorption. Surfactant-surfactant adsorption and competition during repeat AFFF applications that are at concentrations above the CMC resulted in adsorbed PFAS from the first application, changing the nature of the soil surface with preferential sorption of anionic PFAS and release of zwitterionic PFAS due to competitive elution. Applying a polyparameter quantitative structure-property relationship developed to describe sorption of AFFF-derived PFAS to uncontaminated, saturated soil was attempted for our experimental conditions. The model had been derived for data where AFFF is below the apparent CMC and our experimental conditions that included the presence of mixed micelles (aggregates consisting of different kinds of surfactants that exhibit characteristics properties different from micelles composed of a single surfactant) resulted in overall PFAS mass retained by an average of 27.3% ± 2.7% (standard error) above the predicted values. The correlation was significantly improved by adding a "micelle parameter" to account for cases where the applied AFFF was above the apparent CMC. Our results highlight the importance of interactions between the AFFF components that can only be investigated by employing complex PFAS mixtures at concentrations present in actual AFFF at application strength, which are above their apparent CMC. In firefighter-training areas (AFFF source zones), competitive desorption of PFAS may result in downgradient PFAS retention when desorbed PFAS become resorbed to uncontaminated soil.

Oxidative Transformation of Nafion-Related Fluorinated Ether Sulfonates: Comparison with Legacy PFAS Structures and Opportunities of Acidic Persulfate Digestion for PFAS Precursor Analysis.

The total oxidizable precursor (TOP) assay has been extensively used for detecting PFAS pollutants that do not have analytical standards. It uses hydroxyl radicals (HO•) from the heat activation of persulfate under alkaline pH to convert H-containing precursors to perfluoroalkyl carboxylates (PFCAs) for target analysis. However, the current TOP assay oxidation method does not apply to emerging PFAS because (i) many structures do not contain C-H bonds for HO• attack and (ii) the transformation products are not necessarily PFCAs. In this study, we explored the use of classic acidic persulfate digestion, which generates sulfate radicals (SO4-•), to extend the capability of the TOP assay. We examined the oxidation of Nafion-related ether sulfonates that contain C-H or -COO-, characterized the oxidation products, and quantified the F atom balance. The SO4-• oxidation greatly expanded the scope of oxidizable precursors. The transformation was initiated by decarboxylation, followed by various spontaneous steps, such as HF elimination and ester hydrolysis. We further compared the oxidation of legacy fluorotelomers using SO4-• versus HO•. The results suggest novel product distribution patterns, depending on the functional group and oxidant dose. The general trends and strategies were also validated by analyzing a mixture of 100000- or 10000-fold diluted aqueous film-forming foam (containing various fluorotelomer surfactants and organics) and a spiked Nafion precursor. Therefore, (1) the combined use of SO4-• and HO• oxidation, (2) the expanded list of standard chemicals, and (3) further elucidation of SO4-• oxidation mechanisms will provide more critical information to probe emerging PFAS pollutants.

Biotransformation of PFAA Precursors by Oxygenase-Expressing Bacteria in AFFF-Impacted Groundwater and in Pure-Compound Studies with 6:2 FTS and EtFOSE.

Numerous US drinking water aquifers have been contaminated with per- and polyfluoroalkyl substances (PFAS) from fire-fighting and fire-training activities using aqueous film-forming foam (AFFF). These sites often contain other organic compounds, such as fuel hydrocarbons and methane, which may serve as primary substrates for cometabolic (i.e., nongrowth-linked) biotransformation reactions. This work investigates the abilities of AFFF site relevant bacteria (methanotrophs, propanotrophs, octane, pentane, isobutane, toluene, and ammonia oxidizers), known to express oxygenase enzymes when degrading their primary substrates, to biotransform perfluoroalkyl acid (PFAA) precursors to terminal PFAAs. Microcosms containing AFFF-impacted groundwater, 6:2 fluorotelomer sulfonate (6:2 FTS), or N-ethylperfluorooctane sulfonamidoethanol (EtFOSE) were inoculated with the aerobic cultures above and incubated for 4 and 8 weeks at 22 °C. Bottles were sacrificed, extracted, and subjected to target, nontarget, and suspect screening for PFAS. The PFAA precursors 6:2 FTS, N-sulfopropyldimethyl ammoniopropyl perfluorohexane sulfonamide (SPrAmPr-FHxSA), and EtFOSE transformed up to 99, 71, and 93%, respectively, and relevant daughter products, such as the 6:1 fluorotelomer ketone sulfonate (6:1 FTKS), were identified in quantities previously not observed, implicating oxygenase enzymes. This is the first report of a suite of site relevant PFAA precursors being transformed in AFFF-impacted groundwater by bacteria grown on substrates known to induce specific oxygenase enzymes. The data provide crucial insights into the microbial transformation of these compounds in the subsurface.

Characterizing the Areal Extent of PFAS Contamination in Fish Species Downgradient of AFFF Source Zones.

Most monitoring programs next to large per- and polyfluoroalkyl substances (PFAS) sources focus on drinking water contamination near source zones. However, less is understood about how these sources affect downgradient hydrological systems and food webs. Here, we report paired PFAS measurements in water, sediment, and aquatic biota along a hydrological gradient away from source zones contaminated by the use of legacy aqueous film-forming foam (AFFF) manufactured using electrochemical fluorination. Clustering analysis indicates that the PFAS composition characteristic of AFFF is detectable in water and fishes >8 km from the source. Concentrations of 38 targeted PFAS and extractable organofluorine (EOF) decreased in fishes downgradient of the AFFF-contaminated source zones. However, PFAS concentrations remained above consumption limits at all locations within the affected watershed. Perfluoroalkyl sulfonamide precursors accounted for approximately half of targeted PFAS in fish tissues, which explain >90% of EOF across all sampling locations. Suspect screening analyses revealed the presence of a polyfluoroketone pharmaceutical in fish species, and a fluorinated agrochemical in water that likely does not accumulate in biological tissues, suggesting the presence of diffuse sources such as septic system and agrochemical inputs throughout the watershed in addition to AFFF contamination. Based on these results, monitoring programs that consider all hydrologically connected regions within watersheds affected by large PFAS sources would help ensure public health protection.

Stability and Biotransformation of 6:2 Fluorotelomer Sulfonic Acid, Sulfonamide Amine Oxide, and Sulfonamide Alkylbetaine in Aerobic Sludge.

The 6:2 fluorotelomer sulfonamide (6:2 FTSAm)-based compounds signify a prominent group of per- and polyfluoroalkyl substances (PFAS) widely used in contemporary aqueous film-forming foam (AFFF) formulations. Despite their widespread presence, the biotransformation behavior of these compounds in wastewater treatment plants remains uncertain. This study investigated the biotransformation of 6:2 FTSAm-based amine oxide (6:2 FTNO), alkylbetaine (6:2 FTAB), and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) in aerobic sludge over a 100-day incubation period. The biotransformation of 6:2 fluorotelomer sulfonamide alkylamine (6:2 FTAA), a primary intermediate product of 6:2 FTNO, was indirectly assessed. Their stability was ranked based on the estimated half-lives (t1/2): 6:2 FTAB (no obvious products were detected) ≫ 6:2 FTSA (t1/2 ≈28.8 days) > 6:2 FTAA (t1/2 ≈11.5 days) > 6:2 FTNO (t1/2 ≈1.2 days). Seven transformation products of 6:2 FTSA and 15 products of 6:2 FTNO were identified through nontarget and suspect screening using high-resolution mass spectrometry. The transformation pathways of 6:2 FTNO and 6:2 FTSA in aerobic sludge were proposed. Interestingly, 6:2 FTSAm was hardly hydrolyzed to 6:2 FTSA and further biotransformed to perfluoroalkyl carboxylic acids (PFCAs). Furthermore, the novel pathways for the generation of perfluoroheptanoic acid (PFHpA) from 6:2 FTSA were revealed.

Leaching of Perfluoroalkyl Acids during Unsaturated Zone Flushing at a Field Site Impacted with Aqueous Film Forming Foam.

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.

Identifying Unknown Fluorine-Containing Compounds in Environmental Samples Using 19F NMR and Spectral Database Matching.

The ubiquity of per- and polyfluorinated alkyl substances (PFAS) in the environment is a continuing concern. While typical analytical methods for the analysis of PFAS include both targeted and non-targeted mass spectrometry, there remains a significant portion of fluorinated compounds that are not accounted for by these routine methods. It has been previously demonstrated that 19F NMR can be used to identify these compounds, helping to close the mass balance on total fluorine in the environment. 19F NMR offers an unbiased method of analysis that requires no anticipation of fluorine-carbon bonds or functional groups. However, there is resistance to further uptake of NMR spectroscopy as an analytical tool, owing to perceived difficulties in sensitivity and spectral overlap. In this study, we measure the 19F NMR spectrum of hundreds of fluorinated compounds and use this constructed database to determine the concentration of PFAS in an extracted sample of a known aqueous firefighting foam-contaminated site. The 19F NMR database has been included for use by other researchers, and we discuss the intricacies of 19F NMR as applied to environmental samples.

Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams.

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Role of Mineral-Organic Interactions in PFAS Retention by AFFF-Impacted Soil.

A comprehensive, generalized approach to predict the retention of per- and polyfluoroalkyl substances (PFAS) from aqueous film-forming foam (AFFF) by a soil matrix as a function of PFAS molecular and soil physiochemical properties was developed. An AFFF with 34 major PFAS (12 anions and 22 zwitterions) was added to uncontaminated soil in one-dimensional saturated column experiments and PFAS mass retained was measured. PFAS mass retention was described using an exhaustive statistical approach to generate a poly-parameter quantitative structure-property relationship (ppQSPR). The relevant predictive properties were PFAS molar mass, mass fluorine, number of nitrogens in the PFAS molecule, poorly crystalline Fe oxides, organic carbon, and specific (BET-N2) surface area. The retention of anionic PFAS was nearly independent of soil properties and largely a function of molecular hydrophobicity, with the size of the fluorinated side chain as the main predictor. Retention of nitrogen-containing zwitterionic PFAS was related to poorly crystalline metal oxides and organic carbon content. Knowledge of the extent to which a suite of PFAS may respond to variations in soil matrix properties, as developed here, paves the way for the development of reactive transport algorithms with the ability to capture PFAS dynamics in source zones over extended time frames.

Exposure to high levels of PFAS through drinking water is associated with increased risk of type 2 diabetes-findings from a register-based study in Ronneby, Sweden.

BACKGROUND: Epidemiological studies linking type 2 diabetes (T2D) and exposure to per- and polyfluoroalkyl substances (PFAS), are limited and have yielded conflicting results. This register-based study aimed to investigate the risk of T2D among Swedish adults who had been exposed to PFAS from highly contaminated drinking water for decades. METHODS: The study included 55,032 adults (aged ≥18 years) from the Ronneby Register Cohort, who ever lived in Ronneby during 1985-2013. Exposure was assessed using the yearly residential address and the absence ("never-high") or presence ("ever-high") of high PFAS contamination in the municipal drinking water supply; the latter was subdivided into "early-high" and "late-high" exposure with cut-off at 2005. Incident T2D cases were retrieved from the National Patient Register and the Prescription Register. Cox proportional hazard models with time-varying exposure were used to estimate hazard ratios (HRs). Stratified analyses were performed based on age (18-45 vs > 45). RESULTS: Elevated HRs for T2D were observed when comparing "ever-high" to "never-high" exposure (HR 1.18, 95% CI 1.03-1.35), as well as when comparing "early-high" (HR 1.12, 95% CI 0.98-1.50) or "late-high" (HR 1.17, 95% CI 1.00-1.37) to "never-high", after adjusting for age and sex. Individuals aged 18-45 years had even higher HRs. Adjusting for the highest-achieved education level attenuated the estimates, but the directions of associations remained. Elevated HRs were also found among those who had lived in areas with a heavily contaminated water supply for 1-5 years (HR 1.26, 95% CI 0.97-1.63) and 6-10 years (HR 1.25, 95% CI 0.80-1.94). CONCLUSION: This study suggests an increased risk of T2D after long-term high PFAS exposure through drinking water. In particular, a higher risk of early onset diabetes was found, indicating increased susceptibility to PFAS-related health effects at younger ages.

Perfluoroalkyl substances exposure in firefighters: Sources and implications.

Firefighters are at risk of occupational exposure to long-chain per- and poly-fluoroalkyl substances (PFASs), most notably from PFASs present in Class B aqueous film-forming foam (AFFF). Firefighters have been found to have elevated serum levels of long-chain PFASs. Due to the persistence of PFAS chemicals in the human body and their ability to bioaccumulate, firefighters experience the latent and cumulative effects of PFAS-containing AFFF exposure that occurs throughout their careers. This article summarizes the history of AFFF use by firefighters and current AFFF use practices. In addition, this paper describes PFAS levels in firefighter serum, PFAS serum removal pathways, PFAS exposure pathways, and occupational factors affecting PFAS levels in firefighters. International, national, and state agencies have concluded that PFOA, a long-chain PFAS, is potentially carcinogenic and that carcinogens have an additive effect. From the cancer types that may be associated with PFAS exposure, studies on cancer risk among firefighters have shown an elevated risk for thyroid, kidney, bladder, testicular, prostate, and colon cancer. Thus, exposure to PFAS-containing AFFF may contribute to firefighter cancer risk and warrants further research.

Occupational exposure and serum levels of per- and polyfluoroalkyl substances (PFAS): A review.

BACKGROUND: Per- and polyfluoroalkyl substances, or PFAS, are a class of chemicals used in nearly all sectors of industry and many consumer products. Their resistance to degradation, however, means that PFAS are ubiquitous in the environment and bioaccumulate. PFAS exposure has also been linked to a variety of adverse health effects. Occupational PFAS exposure is of particular concern as research on PFAS exposure in worker populations has historically been limited and generally restricted to fluorochemical plant workers involved in PFAS production. METHODS: A comprehensive review of peer-reviewed scientific literature was conducted to investigate which worker populations may experience occupational exposure to PFAS. Serum PFAS levels reported in various occupations were analyzed and compared to serum PFAS levels published on the general public exposed to PFAS-contaminated drinking water and the study population of the National Health and Nutrition Examination Survey (NHANES). RESULTS: Our analysis indicates that professional ski waxers and firefighters may be exposed to several different PFAS at levels often similar to or higher than levels among fluorochemical plant workers and individuals in communities with PFAS-contaminated drinking water, and higher than levels in the general public. PFAS serum level data on other occupations were largely absent. CONCLUSIONS: Results highlight a need for additional research on occupational PFAS exposures and concomitant environmental exposures in these populations. Research on exposure levels in occupations and industries known or suspected to utilize PFAS is critically needed to foster informed recommendations for exposure mitigation measures to protect workers from adverse health effects of PFAS exposure.

Application of Hydrothermal Alkaline Treatment for Destruction of Per- and Polyfluoroalkyl Substances in Contaminated Groundwater and Soil.

Hydrothermal alkaline treatment (HALT) can effectively degrade per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foam (AFFF). However, information is lacking regarding the treatment of PFASs in actual groundwater and soil from AFFF-impacted sites, especially for complex soil matrices. Given the lack of studies on direct soil treatment for PFAS destruction, we herein applied HALT to two groundwater samples and three soil samples from AFFF-impacted sites and characterized the destruction of PFASs using high-resolution mass spectrometry. Results showed that the 148 PFASs identified in all collected field samples, including 10 cationic, 98 anionic, and 40 zwitterionic PFASs, were mostly degraded to nondetectable levels within 90 min when treated with 5 M NaOH at 350 °C. The near-complete defluorination, as evidenced by fluoride release measurements, confirmed the complete destruction of PFASs. While many structures, including perfluoroalkyl carboxylic acids and polyfluorinated substances, were readily degraded, perfluoroalkyl sulfonates (PFSAs, CnF2n+1-SO3-), most notably with short chain lengths (n = 3-5), were more recalcitrant. Rates of PFSA destruction in groundwater samples were similar to those measured in laboratory water solutions, but reactions in soil were slow, presumably due to base-neutralizing properties of the soil. Further, the degradation of PFASs in groundwaters and soils was found to be a function of reaction temperature, NaOH concentration, and reaction time. These findings have important implications for the remediation of AFFF-impacted sites.

Biological and Chemical Transformation of the Six-Carbon Polyfluoroalkyl Substance N-Dimethyl Ammonio Propyl Perfluorohexane Sulfonamide (AmPr-FHxSA).

Sites impacted by aqueous film-forming foam (AFFF) contain co-contaminants that can stimulate biotransformation of polyfluoroalkyl substances. Here, we compare how microbial enrichments from AFFF-impacted soil amended with diethyl glycol monobutyl ether (found in AFFF), aromatic hydrocarbons (present in co-released fuels), acetate, and methane (substrates used or formed during bioremediation) impact the aerobic biotransformation of an AFFF-derived six-carbon electrochemical fluorination (ECF) precursor N-dimethyl ammonio propyl perfluorohexane sulfonamide (AmPr-FHxSA). We found that methane- and acetate-oxidizing cultures resulted in the highest yields of identifiable products (38 and 30%, respectively), including perfluorohexane sulfonamide (FHxSA) and perfluorohexane sulfonic acid (PFHxS). Using these data, we propose and detail a transformation pathway. Additionally, we examined chemical oxidation products of AmPr-FHxSA and FHxSA to provide insights on remediation strategies for AmPr-FHxSA. We demonstrate mineralization of these compounds using the sulfate radical and test their transformation during the total oxidizable precursor (TOP) assay. While perfluorohexanoic acid accounted for over 95% of the products formed, we demonstrate here for the first time two ECF-based precursors, AmPr-FHxSA and FHxSA, that produce PFHxS during the TOP assay. These findings have implications for monitoring poly- and perfluoroalkyl substances during site remediation and application of the TOP assay at sites impacted by ECF-based precursors.

Comparing the Leaching Behavior of Per- and Polyfluoroalkyl Substances from Contaminated Soils Using Static and Column Leaching Tests.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Assessment of Mobilization Potential of Per- and Polyfluoroalkyl Substances for Soil Remediation.

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs (C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs (C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship (R2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

An Integrated Approach for Determination of Total Per- and Polyfluoroalkyl Substances (PFAS).

Per- and polyfluoroalkyl substances (PFAS) are difficult to analyze in environmental media due challenges such as extraction recovery and lack of analytical standards. The total oxidizable precursor (TOP) assay and suspect screening analysis coupled with semiquantitative (SQ) concentration estimates are two approaches to assess total PFAS in environmental media, but studies are needed to optimize workstreams for total PFAS analysis. This study applied two soil extraction methods, TOP assay, and SQ analysis to three aqueous film-forming foams (AFFFs) and three AFFF-impacted soils. In soils, the total PFAS estimated with results from an extraction method utilizing sequential acidic and basic solvents led to a 35% increase in precursors during TOP assay relative to results from a basic solvent only extraction in one of three soils tested, but concentrations did not increase significantly in remaining soils. Furthermore, sample-specific dilution schemes were required to overcome matrix effects caused by the acidic extraction step that influenced estimates of total PFAS by SQ analysis. The results highlight that there is not an advantage to routine application of an acid extraction step in PFAS-impacted soils. In three AFFFs, suspect screening of post-TOP samples identified eight classes of PFAS present after oxidation. Concentrations of three classes increased, suggesting they are new TOP end points. Concentrations of the remaining five classes either remained constant after TOP or exhibited slight decreases. As a result, combined TOP and SQ workstreams may yield the most representative assessment of total PFAS composition and concentration. The eight classes of PFAS present after TOP did not degrade in harsh conditions. Some are structurally similar to PFCAs and PFSAs and are known to occur in the environment, suggesting a similar degree of persistence and a need for more routine monitoring.