AFFF-impacted Sites Research Articles

Zwitterionic, cationic, and anionic PFAS in freshwater sediments from AFFF-impacted and non-impacted sites of Eastern Canada

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFAS) were investigated in freshwater sediments of Canada, including sites impacted by aqueous film-forming foams (AFFFs). The first step of the project involved optimizing the extraction method with equilibrated sediment-water-AFFF samples. The analytical method had acceptable linearity, accuracy, and precision in the sediment matrix, and was further validated with NIST SRM 1936. In the second step of the project, the method was applied to determine over 70 target PFAS in field-collected sediments (n = 102). At federal contaminated sites of Ontario, Newfoundland, and Québec (ditches and creeks at international airports with fire training or fire equipment testing areas), summed PFAS averaged 30ng/g (max of 160ng/g) with molecular patterns dominated by perfluorooctane sulfonate (maximum PFOS: 84ng/g). Based on maximum observed concentrations >10ng/g, other key PFAS at these AFFF-impacted sites included negative ion mode perfluorohexane sulfonate, perfluorohexane sulfonamide, fluorotelomer sulfonates (6:2 FTS and 8:2 FTS) and 5:3 fluorotelomer acid, and positive ion mode N-dimethylammoniopropyl perfluorohexane sulfonamide and 5:1:2 fluorotelomer betaine. In contrast, environmental sediment samples collected at a larger spatial scale (province-wide survey) were characterized by low ΣPFAS (generally <1ng/g), with PFOS/PFOA below chronic toxicity thresholds for aquatic life.

Stimulating Acidimicrobium sp. Strain A6 in iron-rich, acidic sediments from AFFF-impacted sites for PFAS defluorination

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 (NH4+) 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 NH4+ 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 NH4+. 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 NH4+ 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.

PFAS Porewater concentrations in unsaturated soil: Field and laboratory comparisons inform on PFAS accumulation at air-water interfaces

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.

Aerobic biotransformation of 6:2 fluorotelomer sulfonate in soils from two aqueous film-forming foam (AFFF)-impacted sites

Although 6:2 fluorotelomer sulfonate (6:2 FTS) is a common ingredient in aqueous film-forming foam (AFFF) formulations, its environmental fate at AFFF-impacted sites remains poorly understood. This study investigated the biotransformation of 6:2 FTS in microcosms prepared with soils collected from two AFFF-impacted sites; the former Loring Air Force Base (AFB) and Robins AFB. The half-life of 6:2 FTS in Loring soil was 43.3 days; while >60 mol% of initially spiked 6:2 FTS remained in Robins soil microcosms after a 224-day incubation. Differences in initial sulfate concentrations and the depletion of sulfate over the incubation likely contributed to the different 6:2 FTS biotransformation rates between the two soils. At day 224, stable transformation products, i.e., C4C7 perfluoroalkyl carboxylates, were formed with combined molar yields of 13.8 mol% and 1.2 mol% in Loring and Robins soils, respectively. Based on all detected transformation products, the biotransformation pathways of 6:2 FTS in the two soils were proposed. Microbial community analysis suggests that Desulfobacterota microorganisms may promote 6:2 FTS biotransformation via more efficient desulfonation. In addition, species from the genus Sphingomonas, which exhibited higher tolerance to elevated concentrations of 6:2 FTS and its biotransformation products, are likely to have contributed to 6:2 FTS biotransformation. This study demonstrates the potential role of biotransformation processes on the fate of 6:2 FTS at AFFF-impacted sites and highlights the need to characterize site biogeochemical properties for improved assessment of 6:2 FTS biotransformation behavior.

Factors Affecting the Adsorption of Per- and Polyfluoroalkyl Substances (PFAS) by Colloidal Activated Carbon

The immobilization of per- and polyfluoroalkyl substances (PFAS) by colloidal activated carbon (CAC) barriers has been proposed as a potential in-situ method to mitigate the transport of plumes of PFAS in the subsurface. However, if PFAS are continuously released from a source zone, the adsorptive sites on CAC will eventually become saturated, upon which point the breakthrough of PFAS in the barrier will occur. To predict the long-term effectiveness of CAC barriers, it is important to evaluate the factors that may affect the adsorption of PFAS on CAC. In this study, the adsorption of 7 PFAS on a polymer-stabilized CAC (i.e., PlumeStop®) and on a polymer-free CAC was investigated using batch experiments. The adsorption affinity of PFAS to CAC was in the following order: PFOS > 6:2 FTS > PFHxS > PFOA > PFBS > PFPeA > PFBA. This result indicates that hydrophobic interaction was the predominant adsorption mechanism, and that hydrophilic compounds such as PFBA and PFPeA will break through CAC barriers first. The partition coefficient Kd for the adsorption of PFAS on the polymer-stabilized CAC was 1.3 - 3.5 times smaller than the Kd for the adsorption of PFAS on the polymer-free CAC, suggesting that the polymers decreased the adsorption, presumably due to competitive sorption. Thus, the PFAS adsorption capacity of PlumeStop CAC barriers is expected to increase once the polymers are biodegraded and/or washed away. The affinity of PFOS and PFOA to CAC increased when the ionic strength of the solution increased from 1 to 100 mM, or when the concentration of Ca2+ increased from 0 to 2 mM. In contrast, less PFOS and PFOA were adsorbed in the presence of 1 - 20 mgC/L Suwannee River Fulvic Acid, which represented dissolved organic carbon, or in the presence of 10 - 100 mg/L diethylene glycol butyl ether (DGBE), which is an important component in some aqueous film-forming foam (AFFF) formulations. The presence of 0.5 - 4.8 mg/L benzene or 0.5 - 8 mg/L trichloroethylene, the co-contaminants that may comingle with PFAS at AFFF-impacted sites, diminished PFOS adsorption but had no effect or even slightly enhanced PFOA adsorption. When the initial concentration of TCE was 8 mg/L, the Kd (514 ± 240 L/g) for the adsorption of PFOS was approximately 20 times lower than that in the TCE-free system (Kd = 9,579 ± 829 L/g). The results of this study provided insights into some key factors that may affect the adsorption of PFAS in in-situ CAC barriers.

Hydroxyl Radical Transformations of Perfluoroalkyl Acid (PFAA) Precursors in Aqueous Film Forming Foams (AFFFs).

Historical releases of aqueous film forming foam (AFFF) are significant sources of poly- and perfluoroalkyl substances (PFASs), including perfluoroalkyl acids (PFAAs) and their precursors, to the environment. While several studies have focused on microbial biotransformation of polyfluorinated precursors to PFAAs, the role of abiotic transformations at AFFF-impacted sites is less clear. Herein, we use photochemically generated hydroxyl radical to demonstrate that environmentally relevant concentrations of hydroxyl radical (•OH) can play a significant role in these transformations. High-resolution mass spectrometry (HRMS) was used to perform targeted analysis, suspect screening, and nontargeted analyses, which were used to identify the major products of AFFF-derived PFASs as perfluorocarboxylic acids, though several potentially semi-stable intermediates were also observed. Using competition kinetics in a UV/H2O2 system, hydroxyl radical rate constants (kOH) for 24 AFFF-derived polyfluoroalkyl precursors were measured to be 0.28 to 3.4 × 109 M-1 s-1. Differences in kOH were observed for compounds with differing headgroups and perfluoroalkyl chain lengths. Also, differences in kOH measured for the only relevant precursor standard available, n-[3-propyl]tridecafluorohexanesulphonamide (AmPr-FHxSA), as compared to AmPr-FHxSA present in AFFF suggest that intermolecular associations in the AFFF matrix may affect kOH. Considering environmentally relevant [•OH]ss, polyfluoroalkyl precursors are expected to exhibit half-lives of ∼8 days in sunlit surface waters and possibly as short as ∼2 h during oxygenation of Fe(II)-rich subsurface systems.

Effect of geochemical conditions on PFAS release from AFFF-impacted saturated soil columns.

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.

Assessing aerobic biotransformation of 8:2 fluorotelomer alcohol in aqueous film-forming foam (AFFF)-impacted soils: Pathways and microbial community dynamics

Production of 8:2 fluorotelomer alcohol (8:2 FTOH) for industrial and consumer products, including aqueous film-forming foams (AFFFs) used for firefighting, has resulted in its widespread occurrence in the environment. However, the fate of 8:2 FTOH at AFFF-impacted sites remains largely unknown. Using AFFF-impacted soils from two United States Air Force Bases, microcosm experiments evaluated the aerobic biotransformation of 8:2 FTOH (extent and byproduct formation) and the dose-response on microbial communities due to 8:2 FTOH exposure. Despite different microbial communities, rapid transformation of 8:2 FTOH was observed during a 90-day incubation in the two soils, and 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were detected as major transformation products. Novel transformation products, including perfluoroalkane-like compounds (1H-perfluoroheptane, 1H-perfluorohexane, and perfluoroheptanal) were identified by liquid chromatography-high resolution mass spectrometry (LC-HRMS) and used to develop aerobic 8:2 FTOH biotransformation pathways. Microbial community analysis suggests that species from genus Sphingomonas are potential 8:2 FTOH degraders based on increased abundance in both soils after exposure, and the genus Afipia may be more tolerant to and/or involved in the transformation of 8:2 FTOH at elevated concentrations. These findings demonstrate the potential role of biological processes on PFAS fate at AFFF-impacted sites through fluorotelomer biotransformation.

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.

The occurrence, distribution, and risks of PFAS at AFFF-impacted sites in Finland

Per- and polyfluoroalkyl substances (PFAS) comprise a wide group of persistent chemicals, whose ubiquitous occurrence in the environment, particularly due to their extensive use for fire suppression in aqueous film forming foams (AFFFs), has raised global attention. We evaluated the impacts of PFAS at three firefighting training sites and one industrial site in Finland, to highlight key elements to be considered in the retrospective risk assessment of these chemicals. The site assessments covered the occurrence and distribution of 23 PFAS in multiple environmental matrices, i.e., soil, sediment, surface water, groundwater, and biota, and the subsequent risks to human health and the environment owing to the migration of and exposure to the selected compounds. Our study showed that the extensive use of nowadays restricted or substituted PFAS, particularly PFOS, are still often the predominant compounds detected at AFFF-impacted sites and will continue to cause long-term risks to the environment. The most significant environmental or health risks at these sites are likely to concern aquatic ecosystems, fish consumption or groundwater usage due to the off-site migration of PFAS. Here, even a single fire extinguishing event can be a considerable contributor. We also illustrate that conventional procedures based on simple mass-balance, and exposure models, with a focus on PFOS and other site-specifically relevant PFAS may provide sufficient means to assess the risks. Moreover, we address that despite the exceedance of the very stringent regulatory threshold values issued recently for PFAS, the actual site-specific risks to human health and the environment may remain reasonably low.

Per- and Polyfluoroalkyl Substances in Contaminated Soil and Groundwater at Airports: A Canadian Case Study.

The occurrence of 93 classes of per- and polyfluoroalkyl substances (PFASs) was investigated at aqueous film-forming foam (AFFF)-impacted sites of four Canadian airports. Surface/subsurface soil and groundwater samples were characterized using high-resolution mass spectrometry (HRMS) and an improved total oxidizable precursor (TOP) assay. PFAS profiles, loads, and spatial trends were highly site-specific, influenced by the AFFF use history, variations in sorption, transport, and in situ transformation potential of PFASs. All sites have been impacted by more than one AFFF chemistry, with the active firefighter training area exhibiting a greater PFAS variety and total PFAS burden than decommissioned sites. Zwitterionic and cationic compounds composed a large percentage (34.5-85.5%) of the total PFAS mass in most surface soil samples in the source zone but a relatively low percentage (<20%) in groundwater samples. Background soils surrounding the source zone contained predominantly unidentified precursors attributed to atmospheric deposition, while in AFFF-impacted soils, precursors originating from AFFFs can be largely captured by HRMS using available suspect lists. Horizontal transfer of PFASs in surface soils was limited, but vertical migration down the soil column occurred even in locations of low permeability. This study provides a critical data set to support developing new priority analyte lists and integrating TOP assay for comprehensive PFAS monitoring at AFFF-impacted sites.

The Case for Direct Measures of Soil-to-Groundwater Contaminant Mass Discharge at AFFF-Impacted Sites.

Many entities around the world are initiating massive field campaigns to characterize the environmental distribution of per- and polyfluoroalkyl substances (PFAS), particularly at aqueous film-forming foam (AFFF) impacted sites where historic point-source discharges occurred at the ground surface. Concurrently, many regulatory agencies are publishing criteria used in practice to define the "nature and extent" of PFAS-impacted environmental media. Specific to the soil-to-groundwater transport pathway protective of the groundwater ingestion end point, these soil criteria (or screening values) are to date exclusively based on the traditional approach used for hydrophobic organics with a number of simplifying assumptions. Research has clearly contradicted these assumptions, yet alternative methodologies have yet to emerge from the literature. This Perspective provides a rationale for why alternative approaches are critically necessary and proposes the application of lysimetry as a practical solution to accurately assess PFAS transport within unsaturated vadose zone soils. Ultimately, there is an urgent need to justify soil remediation on the basis of groundwater protection and to prioritize remedial efforts in order to optimize limited fiscal resources.

Per‐ and Polyfluoroalkyl Substances (PFAS) in Surface Water Near US Air Force Bases: Prioritizing Individual Chemicals and Mixtures for Toxicity Testing and Risk Assessment

Per- and polyfluoroalkyl substances (PFAS) are a large class of persistent chemicals used for decades in industrial and commercial applications. A key challenge with regard to estimating potential risk to ecological (and human) receptors associated with PFAS exposure lies in the fact that there are many different PFAS compounds and several to many can co-occur in any given environmental sample. We applied a data science approach to characterize and prioritize PFAS and PFAS mixtures from a large dataset of PFAS measurements in surface waters associated with US Air Force Installations with a history of the use of aqueous film-forming foams (AFFFs). Several iterations of stakeholder feedback culminated in a few main points that advanced our understanding of a complex dataset and the larger ecotoxicological problem. First, perfluorooctane sulfonate (PFOS) was often a dominant PFAS in a given surface water sample, frequently followed by perfluorohexane sulfonate (PFHxS). Second, a 4-chemical mixture generally accounted for >80% of the sum of all routinely reported PFAS in a sample, and the most representative 4-chemical mixture was composed of PFOS, PFHxS, perfluorohexanoic acid (PFHxA), and perfluorooctanoic acid (PFOA). We suggest that these results demonstrate the utility of formalized data science analysis and assessment frameworks to address complex ecotoxicological problems. Specifically, our example dataset results can be used to provide perspective on toxicity testing, ecological risk assessments, and field studies of PFAS in and around AFFF-impacted sites. Environ Toxicol Chem 2021;40:871-882. © 2020 SETAC.

A Mathematical Model for the Release, Transport, and Retention of Per- and Polyfluoroalkyl Substances (PFAS) in the Vadose Zone.

Per- and Polyfluoroalkyl Substances (PFAS) are emerging contaminants of critical concern. As surfactants, PFAS tend to accumulate at air-water interfaces and may stay in the vadose zone for long times before contaminating groundwater. Yet not well understood, the extent of retention in the vadose zone has critical implications for risk management and remediation strategies. We present the first mathematical model that accounts for surfactant-induced flow and solid-phase and air-water interfacial adsorption. We apply the model to simulate PFOS (a PFAS compound of primary concern) transport in the vadose zone at a model fire-training area site impacted by Aqueous Film-Forming Foam (AFFF). Air-water interfacial adsorption is shown to have a significant impact-amplified by the low water content due to gravity drainage-total retardation factors range from 233 to 1355 for the sand and 146 to 792 for the soil used in the study. The simulations illustrate it can take several decades or longer for PFOS to reach groundwater. Counterintuitively, the lower water content in the sand-due to stronger drainage and weaker capillary retention-leads to retardation factors greater than for the soil. Also, most PFOS is adsorbed at air-water interfaces with only 1-2% in the aqueous phase. The implications include 1) fine-texture materials could have lower retardation factors than sand due to higher retained water content, 2) soil PFAS concentrations are likely to be orders of magnitude higher than those in groundwater at source zones. Both implications are consistent with recent field observations at hundreds of AFFF-impacted sites.

Sorption of Polyfluoroalkyl Surfactants on Surface Soils: Effect of Molecular Structures, Soil Properties, and Solution Chemistry.

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFASs) are identified in aqueous film-forming foam (AFFF) concentrates and AFFF-impacted sites. However, the mobility potential of zwitterionic and cationic PFASs is poorly understood, preventing reliable site assessment. The study aimed to elucidate the mobility behaviors of PFASs of various charge states in saturated soil-water systems and assess critical influencing factors. Five anionic, three zwitterionic, and one cationic PFASs were investigated in five soils through batch sorption experiments. Pairwise comparison revealed that the quaternary ammonium group imparted a strong affinity of cationic perfluorooctaneamide ammonium compound (PFOAAmS) for soils. The influence of the quaternary ammonium group is mitigated in polyfluoroalkyl betaines, yet perfluorooctane sulfonamidoalkyl betaine (PFOSB) showed strong sorption in selected soils. Two soil bulk properties showed some correlations with the soil-water distribution coefficient (Kd). A positive correlation with the fraction of soil organic carbon was found only for anionic PFASs, whereas cation exchange capacity had an approximate positive correlation with Kd only for PFOAAmS. Water chemistry (Ca2+ and pH) influences the sorption of nonanionic PFASs in very distinct fashions or even in opposite trends to what was known for anionic PFASs. Sorption was insensitive to pH changes except for PFOSB; PFOSB underwent profound sorption reduction because its speciation occurs around neutral pH, while the two other betaines and PFOAAmS have pKa values that are outside of the environmentally relevant range. The lack of correlations suggests that the transport potential of PFASs is probably highly site-specific. It remains a challenge in deciphering PFAS sorption mechanisms and predicting how AFFF plumes migrate.

Optimization of extraction methods for comprehensive profiling of perfluoroalkyl and polyfluoroalkyl substances in firefighting foam impacted soils

The comprehensive analysis of aqueous film forming foam (AFFF) formulations has led in recent years to the discovery of novel classes of perfluoroalkyl and polyfluoroalkyl substances (PFASs). Whether the pre-existing analytical methods for historically monitored PFASs, including perfluorooctane sulfonate (PFOS), could be transferable to a large breadth of newly identified PFASs remains, however, an open question. Data from various lines of evidence indicate that current extraction procedures previously validated with anionic and neutral PFASs may seriously underperform for many cationic and zwitterionic PFASs. The extraction efficiency and instrumental response could be strongly matrix-dependent, which may preclude a robust analysis. The present study sought to investigate a suitable sample preparation procedure for the analysis of anionic, cationic, and zwitterionic PFASs in soil samples. In total, 86 PFASs, representing 24 chemical classes previously discovered in AFFF formulations or at AFFF-impacted sites, were evaluated. The merits and limitations of various extraction media were examined using an AFFF-impacted field-weathered loam soil, as well as a background loam soil amended with AFFFs in-house. Methanol with hydrochloric acid provided excellent recoveries for most cationic and zwitterionic PFASs, including fluorotelomer sulfonamidoalkyl betaines (e.g., 6:2 FTAB) and fluorotelomer betaines (e.g., 9:1:2 FTB), yet performed less satisfactorily for certain anionic PFASs, and may also cause conversion of some PFASs. Sequential extractions using methanol with ammonium acetate exhibited limited matrix effects and suitable recoveries of PFASs from soils of diverse textural classes and organic matter content. The newly-developed extraction method presented the best option for future in-depth characterization of PFASs at AFFF-impacted sites.

Sorption and desorption of anionic, cationic and zwitterionic polyfluoroalkyl substances by soil organic matter and pyrogenic carbonaceous materials

The fraction of pyrogenic carbonaceous materials (PCMs) left in aqueous film-forming foams (AFFFs) source zones may strongly affect the persistence of perfluoroalkyl and polyfluoroalkyl substances (PFASs). To examine the hypothesis and gain an additional perspective on the potential contributions of different organic phases present in soil, we measured sorption and desorption of five AFFF relevant PFASs, one cationic (perfluoroctaneamido ammonium iodide, PFOAAmS), two anionic (perfluorooctane sulfonate, PFOS; perfluorooctanoic carboxylate, PFOA), and two zwitterionic (perfluorooctane amido betaine, PFOAB; 6:2 fluorotelomer sulfonamido betaine, 6:2 FTAB), by three types of PCMs (biochar, soot, and oil-free soot) and soil organic matter (SOM, presented by Pahokee peat) by single-solute batch sorption experiments. It was found that sorption to PCMs is substantially stronger and nonlinear than SOM, especially for the cationic PFOAAmS. Strong sorption to PCMs discovered in this study suggests that such phenomenon can lead to high retardation of PFASs in the AFFF source zone and decreased mobility of PFASs in groundwater, especially for the precursor compounds to the legacy perfluoroalkyl acids. Fouling of PCMs by unburnt oil would hinder the surface activity of PCMs and consequently lower the sorption of PFAS, thereby facilitating PFAS mobility. Moreover, sorption hysteresis was observed in all the systems with sorption of 6:2 FTAB by biochar being the most significant. This study for the first time provided the evidence that PCMs are potentially a significant sink of PFASs in AFFF-impacted sites.

Certain Perfluoroalkyl and Polyfluoroalkyl Substances Associated with Aqueous Film Forming Foam Are Widespread in Canadian Surface Waters.

The presence of perfluoroalkyl and polyfluoroalkyl substances (PFASs) commonly associated with aqueous film forming foams (AFFFs) at sites without known AFFF contamination is a largely unexplored area, which may reveal widespread environmental contaminants requiring further investigation. Sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) screening for 23 classes of PFASs, followed by quantitative analysis was used to investigate surface waters from rural, urban, and AFFF-impacted sites in Canada. The PFASs detected included perfluorohexane sulfonamide (FHxSA), 6:2 fluorotelomer sulfonamide (FTSAm), fluorotelomer sulfonamide alkylbetaines (FTABs), fluorotelomer betaines (FTBs), 6:2 fluorotelomer mercaptoalkylamido sulfonate sulfone (FTSAS-SO2), 6:2 fluorotelomerthiohydroxyl ammonium sulfoxide (FTSHA-SO), 6:2 fluorotelomer sulfonamide alkylamine (FTAA) and C3 to C6 perfluoroalkane sulfonamido amphoterics. Detection of FHxSA in all urban and AFFF-impacted sites (0.04-19 ng/L) indicates the widespread presence of rarely considered perfluorohexanesulfonate (PFHxS) precursors in Canadian waters. FTABs and FTBs were especially abundant with up to 16-33 ng/L of 6:2 FTAB in urban and AFFF-impacted water suggesting it may have additional applications, while FTBs were only in AFFF-impacted sites (qualitative; ∑FTBs 80 ng/L). The distributions of PFASs moving downstream along the AFFF-impacted Welland River and between water and sediment suggested differences in the persistence of various AFFF components and enhanced sorption of long-chain fluorotelomer betaines. Total organofluorine combustion-ion chromatography (TOF-CIC) revealed that fluorotelomer betaines were a substantial portion of the organofluorine in some waters and 36-99.7% of the total organofluorine was not measured in the targeted analysis.

Assessment of the Influence of Soil Characteristics and Hydrocarbon Fuel Cocontamination on the Solvent Extraction of Perfluoroalkyl and Polyfluoroalkyl Substances.

Sites impacted by the use of aqueous film-forming foams (AFFFs) present elevated concentrations of perfluoroalkyl and polyfluoroalkyl substances (PFAS). The characterization of the PFAS contamination at such sites may be greatly complicated by the presence of hydrocarbon cocontaminants and by the large variety of PFAS potentially present in AFFFs. In order to further a more comprehensive characterization of AFFF-contaminated soils, the solvent extraction of PFAS from soil was studied under different conditions. Specifically, the impact of soil properties (textural class, organic matter content) and the presence of hydrocarbon contamination (supplemented in the form of either diesel or crude oil) on PFAS recovery performance was evaluated for two extraction methods [methanol/sodium hydroxide (MeOH/NaOH) and methanol/ammonium hydroxide (MeOH/NH4OH)]. While both methods performed satisfactorily for perfluoroalkyl acids and fluorotelomer sulfonates, the extraction of newly identified surfactants with functionalities such as betaine and quaternary ammonium was improved with the MeOH/NaOH based method. The main factors that were found to influence the extraction efficiency were the soil properties; a high organic matter or clay content was observed to negatively affect the recovery of the newly identified compounds. While the MeOH/NaOH solvent yielded more efficient recovery rates overall, it also entailed the disadvantage of presenting higher detection limits and substantial matrix effects at the instrumental analysis stage, requiring matrix-matched calibration curves. The results discussed herein bear important implications for a more comprehensive and reliable environmental monitoring of PFAS components at AFFF-impacted sites.

Occurrence of select perfluoroalkyl substances at U.S. Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties

The use of aqueous film-forming foam (AFFF) to extinguish hydrocarbon-based fires is recognized as a significant source of environmental poly- and perfluoroalkyl substances (PFASs). Although the occurrence of select PFASs in soil and groundwater at former fire-training areas (FTAs) at military installations operable since 1970 has been consistently confirmed, studies reporting the occurrence of PFASs at other AFFF-impacted sites (e.g. emergency response locations, AFFF lagoons, hangar-related AFFF storage tanks and pipelines, and fire station testing and maintenance areas) are largely missing from the literature. Further, studies have mostly focused on a single site (i.e., FTAs at military installations) and, thus, lack a comparison of sites with diverse AFFF release history. Therefore, the purpose of this investigation was to evaluate select PFAS occurrence at non-FTA sites on active U.S. Air Force installations with historic AFFF use of varying magnitude. Concentrations of fifteen perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (PFOSA), an important PFOS precursor, were measured from several hundred samples among multiple media (i.e., surface soil, subsurface soil, sediment, surface water, and groundwater) collected from forty AFFF-impacted sites across ten installations between March and September 2014, representing one of the most comprehensive datasets on environmental PFAS occurrence to date. Differences in detection frequencies and observed concentrations due to AFFF release volume are presented along with rigorous data analyses that quantitatively demonstrate phase-dependent (i.e., solid-phase vs aqueous-phase) differences in the chemical signature as a function of carbon chain-length and in situ PFOS (and to a slightly lesser extent PFHxS) formation, presumably due to precursor biotransformation.