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Urban stormwater runoff is considered a key component of future water supply portfolios for water-stressed cities. Beneficial use of runoff, such as capture for recharge of drinking water aquifers, relies on improved stormwater treatment. Many dissolved constituents, including metals and trace organic contaminants (TrOCs) such as hydrophilic pesticides and poly- and perfluoroalkyl substances (PFASs), are of concern due to their toxicity, persistence, prevalence in stormwater runoff, and poor removal in conventional stormwater control measures. This study explores the operational flow rate limitations of black carbon (BC)-amended engineered media filters for removal of a wide suite of dissolved metals and TrOCs and provides validation for a previously developed predictive TrOC transport model. Column experiments were conducted with face velocities of 40 and 60 cm h -1 to assess Douglas Fir-based biochar and regenerated activated carbon (RAC) filter performance in light of media-contaminant removal kinetic limitations. This study found that increasing the face velocity in BC-amended filters to 40 and 60 cm h -1 , which are representative of field conditions, decreased the removal of total suspended solids, turbidity, dissolved hydrophilic TrOCs, and PFASs when expressed as volume treated relative to previous studies conducted at 20 cm h -1 . Dissolved metals and hydrophobic TrOCs removal were not substantially affected by the increased flow rates. A predictive 1-d intraparticle pore diffusion-limited sorption model with sorption and effective tortuosity parameters determined previously from experiments conducted at 20 cm h -1 was validated for these higher flow rates. This work provides insights to the kinetic limitations of contaminant removal within biochar and RAC filters and implications for stormwater filter design and operation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The long-term leaching of polyfluoroalkyl substances (PFAS) within the vadose zone of an AFFF application site for which the depth to groundwater is approximately 100 m was investigated by characterizing the vertical distribution of PFAS in a high spatial resolution. The great majority (99%) of PFAS mass resides in the upper 3 m of the vadose zone. The depths to which each PFAS migrated, quantified by moment analysis, is an inverse function of molar volume, demonstrating chromatographic separation. The PFAS were operationally categorized into three chain-length groups based on the three general patterns of retention observed. The longest-chain (>∼335 cm 3 /mol molar volume) PFAS remained within the uppermost section of the core, exhibiting minimal leaching. Conversely, the shortest-chain (<∼220 cm 3 /mol) PFAS accumulated at the bottom of the interval, which coincides with the onset of a calcic horizon. PFAS with intermediate-chain lengths were distributed along the length of the core, exhibiting differential magnitudes of leaching. The minimal or differential leaching observed for the longest- and intermediate-chain-length PFAS, respectively, demonstrates that retention processes significantly impacted migration. The accumulation of shorter-chain PFAS at the bottom of the core is hypothesized to result from limited deep infiltration and potential-enhanced retention associated with the calcic horizon.

Monitoring contamination from per- and polyfluoroalkyl substances (PFASs) in water systems impacted by aqueous film-forming foams (AFFFs) typically addresses a few known PFAS groups. Given the diversity of PFASs present in AFFFs, current analytical approaches do not comprehensively address the range of PFASs present in these systems. A suspect-screening and nontarget analysis (NTA) approach was developed and applied to identify novel PFASs in groundwater samples contaminated from historic AFFF use. A total of 88 PFASs were identified in both passive samplers and grab samples, and these were dominated by sulfonate derivatives and sulfonamide-derived precursors. Several ultrashort-chain (USC) PFASs (≤C 3 ) were detected, 11 reported for the first time in Australian groundwater. Several transformation products were identified, including perfluoroalkane sulfonamides (FASAs) and perfluoroalkane sulfinates (PFASis). Two new PFASs were reported (((perfluorohexyl)sulfonyl)sulfamic acid; m / z 477.9068 and ( E )-1,1,2,2,3,3,4,5,6,7,8,8,8-tridecafluorooct-6-ene-1-sulfonic acid; m / z 424.9482). This study highlights that several PFASs are overlooked using standard target analysis, and therefore, the potential risk from all PFASs present is likely to be underestimated.

While foam fractionation (FF) process has emerged as a promising technology for removal of per- and polyfluoroalkyl substances (PFASs) from contaminated groundwater, management of the resulting foam concentrates with elevated concentrations of PFASs (e.g., >1 g/L) remains a challenge. Here, we applied hydrothermal alkaline treatment (HALT) to two foam concentrates derived from FF field demonstration projects that treated aqueous film-forming foam (AFFF)-impacted groundwater. Results showed >90% degradation and defluorination within 90 min of treatment (350 °C, 1 M NaOH) of all 62 PFASs (including cations, anions, and zwitterions) identified in foam concentrates. Observed rate constants for degradation of individual perfluoroalkyl sulfonates (PFSAs, C n F 2 n +1 -SO 3 - ), the most recalcitrant class of PFASs, in both foam concentrates were similar to values measured previously in other aqueous matrices, indicating that elevated initial PFAS concentrations (e.g., PFHxS init = 0.55 g/L), dissolved organic carbon (DOC; up to 4.5 g/L), and salt levels (e.g., up to 325 mg/L chloride) do not significantly affect PFAS reaction kinetics. DOC was partially mineralized by treatment, but a fraction (∼15%) was recalcitrant. Spectroscopic characterization revealed molecular features of the HALT-recalcitrant DOC fraction, and nontarget high-resolution mass spectrometry tentatively identified 129 nonfluorinated HALT-recalcitrant molecules. Analysis of process energy requirements shows that treating PFAS-contaminated foam concentrates with HALT would add minimally (<5%) to the overall energy requirements of an integrated FF-HALT treatment train.

This study elucidates per- and polyfluoroalkyl substance (PFAS) fingerprints for specific PFAS source types. Ninety-two samples were collected from aqueous film-forming foam impacted groundwater (AFFF-GW), landfill leachate, biosolids leachate, municipal wastewater treatment plant effluent (WWTP), and wastewater effluent from the pulp and paper and power generation industries. High-resolution mass spectrometry operated with electrospray ionization in negative mode was used to quantify up to 50 target PFASs and screen and semi-quantify up to 2,266 suspect PFASs in each sample. Machine learning classifiers were used to identify PFASs that were diagnostic of each source type. Four C5-C7 perfluoroalkyl acids and one suspect PFAS (trihydrogen-substituted fluoroethernonanoic acid) were diagnostic of AFFF-GW. Two target PFASs (5:3 and 6:2 fluorotelomer carboxylic acids) and two suspect PFASs (4:2 fluorotelomer-thia-acetic acid and N -methylperfluoropropane sulfonamido acetic acid) were diagnostic of landfill leachate. Biosolids leachates were best classified along with landfill leachates and N -methyl and N -ethyl perfluorooctane sulfonamido acetic acid assisted in that classification. WWTP, pulp and paper, and power generation samples contained few target PFASs, but fipronil (a fluorinated insecticide) was diagnostic of WWTP samples. Our results provide PFAS fingerprints for known sources and identify target and suspect PFASs that can be used for source allocation.

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/H 2 O 2 system, hydroxyl radical rate constants ( k OH ) for 24 AFFF-derived polyfluoroalkyl precursors were measured to be 0.28 to 3.4 × 10 9 M -1 s -1 . Differences in k OH were observed for compounds with differing headgroups and perfluoroalkyl chain lengths. Also, differences in k OH 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 k OH . 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.

Drinking water can be a major source of poly- and perfluoroalkyl substance (PFAS) exposure for humans. The lack of historic data on PFAS drinking-water concentrations and consumption patterns are a limiting factor for developing estimates of past exposure. Here, in contribution to a community-scale PFAS health effects study near fire training facilities that contaminated a local aquifer with PFASs, we present a novel water-infrastructure, mass-balance mixing model coupled to a non-steady state, single-compartment toxicokinetic model that used Monte Carlo simulations to estimate the start of PFAS exposure in drinking water for individuals within three PFAS-impacted communities in El Paso County, Colorado. Our modeling focused on perfluorohexane sulfonic acid (PFHxS) because median serum PFHxS concentrations in a sample of local residents ( n = 213) were twelve times the median observed in the U.S. National Health and Nutrition Examination Survey (2015-2016). Modeling results for study participants were grouped according to their community of residence, revealing a median start of exposure for the town of Fountain of 1998 (25-75% interquartile range [IQR], 1992 to 2010), 2006 (IQR 1995 to 2012) for Security, and 2009 (IQR 1996-2012) for Widefield. Based on the towns' locations relative to an identified hydraulically upgradient PFAS source, the modeled exposure sequencing does not completely align with this conceptual flow model, implying the presence of an additional PFAS source for the groundwater between Widefield and Fountain.

Advanced reduction processes (ARPs) that generate hydrated electrons (e aq - ; e.g., UV-sulfite) have emerged as a promising remediation technology for recalcitrant water contaminants, including per- and polyfluoroalkyl substances (PFASs). The effectiveness of ARPs in different natural water matrices is determined, in large part, by the presence of non-target water constituents that act to quench e aq - or shield incoming UV photons from the applied photosensitizer. This study examined the pH-dependent quenching of e aq - by ubiquitous dissolved carbonate species (H 2 CO 3 *, HCO 3 - , and CO 3 2- ) and quantified the relative importance of carbonate species to other abundant quenching agents (e.g., H 2 O, H + , HSO 3 - , and O 2(aq) ) during ARP applications. Analysis of laser flash photolysis kinetic data in relation to pH-dependent carbonate acid-base speciation yields species-specific bimolecular rate constants for e aq - quenching by H 2 CO 3 *, HCO 3 - , and CO 3 2- ( k H 2 C O 3 * = 2.23 ± 0.42 × 10 9 M -1 s -1 , k H C O 3 - = 2.18 ± 0.73 × 10 6 M -1 s -1 , and k C O 3 2 - = 1.05 ± 0.61 × 10 5 M -1 s -1 ), with quenching dominated by H 2 CO 3 * (which includes both CO 2(aq) and H 2 CO 3 ) at moderately alkaline pH conditions despite it being the minor species. Attempts to apply previously reported rate constants for e aq - quenching by CO 2(aq) , measured in acidic solutions equilibrated with CO 2(g) , overpredict quenching observed in this study at higher pH conditions typical of ARP applications. Moreover, kinetic simulations reveal that pH-dependent trends reported for UV-sulfite ARPs that have often been attributed to e aq - quenching by varying [H + ] can instead be ascribed to variable acid-base speciation of dissolved carbonate and the sulfite sensitizer.

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

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

This paper aims to describe the performance of a soil washing plant (SWP) for remediating a per- and poly-fluoroalkyl substances (PFASs)-contaminated soil with a high clay content (61%). The SWP used both physical and chemical processes; fractionation of the soil particles by size and partitioning of PFASs into the aqueous phase to remove PFASs from the soil. Contaminated water was treated in series with granulated activated carbon (GAC) and ion-exchange resin and reused within the SWP. Approximately 2200 t (dry weight) of PFAS-contaminated soil was treated in 25 batches of 90 t each, with a throughput of approximately 11 t soil/hr. Efficiency of the SWP was measured by observed decreases in total and leachable concentrations of PFASs in the soil. Average removal efficiencies (RE) were up to 97.1% for perfluorocarboxylic acids and 94.9% for perfluorosulfonic acids. REs varied among different PFASs depending on their chemistry (functional head group, carbon chain length) and were independent of the total PFAS concentrations in each soil batch. Mass balance analysis found approximately 90% of the PFAS mass in the soil was transferred to the wash solution and > 99.9% of the PFAS mass in the wash solution was transferred onto the GAC without any breakthrough., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Charles Grimison reports a relationship with Ventia Services that includes: employment., (Crown Copyright © 2022. Published by Elsevier B.V. All rights reserved.)

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.

Per- and polyfluoroalkyl substances (PFASs) are synthetic chemicals that are ubiquitous in environmental and biological systems, including human serum. PFASs are used in many products and industrial processes and are tied to numerous health effects. Due to multiple sources and exposure pathways, methods are needed to identify PFAS sources in communities to develop targeted interventions. We assessed effectiveness of three source apportionment methods (UNMIX, positive matrix factorization [PMF], and principal component analysis - multiple linear regression [PCA-MLR]) for identifying contributors to human serum PFAS concentrations in two highly exposed populations in Colorado and North Carolina where drinking water was contaminated via upstream sources, including a Space Force base and a fluorochemical manufacturing plant. UNMIX and PMF models extracted three to four potential PFAS exposure sources in the Colorado and North Carolina cohorts while PCA-MLR classified two in each cohort. No sources were characterized in NHANES (National Health and Nutrition Examination Study). Results suggest that these three methods can successfully identify sources in highly exposed populations. Future PFAS exposure research should focus on analyzing serum for an expanded PFAS panel, identifying cohorts with other distinct point source exposures, and combining biological and environmental data to better understand source apportionment results in the context of PFAS toxicokinetic behavior., Competing Interests: Declaration of competing interest This work was supported by the National Institute of Environmental Health Sciences (NIEHS) under Grants No. R21ES029394 (CO), T32ES007046, 1R21ES029353 & P42ES031009 (NC) and the Environmental Protection Agency under Grant No. G18A112656081. Any opinion, findings, conclusions, or recommendations expressed are those of the authors and do not necessarily reflect the views of the NIH or the EPA. This publication was developed under Assistance Agreement No. R839482 awarded by the U.S. Environmental Protection Agency to Dr. Christopher P. Higgins., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

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.

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

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

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 ( R 2 = 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.

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

Per- and polyfluoroalkyl substances (PFASs) used in aqueous film-forming foam (AFFF) comprise some perfluoroalkyl substances but a larger variety of polyfluoroalkyl substances. Despite their abundance in AFFF, information is lacking on the potential transformation of these polyfluoroalkyl substances. Due to the biological and chemical stability of the repeating perfluoroalkyl -(CF 2 ) n - moiety common to all known AFFF-derived PFASs, it is not immediately evident whether the microbial biotransformation mechanisms observed for other organic contaminants also govern the microbial biotransformation of polyfluoroalkyl substances. Herein, we aim to: 1) review the literature on the aerobic or anaerobic microbial biotransformation of AFFF-derived polyfluoroalkyl substances in environmental media; 2) compile and summarize proposed microbial biotransformation pathways for major classes of polyfluoroalkyl substances; 3) identify the dominant biotransformation intermediates and terminal biotransformation products; and 4) discuss these findings in the context of environmental monitoring and source allocation. This analysis revealed that much more is currently known about aerobic microbial biotransformation of polyfluoroalkyl substances, as compared to anaerobic biotransformation. Further, there are some similarities in microbial biotransformations of fluorotelomer and electrochemical fluorination-derived polyfluoroalkyl substances, but differences may be largely due to head group composition. Dealkylation, oxidation, and hydrolytic reactions appear to be particularly important for microbial biotransformation of AFFF-derived polyfluoroalkyl substances, and these biotransformations may lead to formation of some semi-stable intermediates. Finally, this review discusses key knowledge gaps and opportunities for further research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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

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, C n F 2 n +1 -SO 3 - ), 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.

Aqueous film-forming foams (AFFFs) are important sources of per- and polyfluoroalkyl substances (PFASs) in soil, groundwater, and surface water. Soil microorganisms can convert polyfluorinated substances into persistent perfluoroalkyl acids, but the understanding of co-contaminant stimulation or inhibition of PFASs biotransformation is limited. In this study, we investigate how aerobic biotransformation of polyfluorinated substances was affected by common AFFF co-contaminants, such as gasoline aromatics: benzene, toluene, ethylbenzene, and o -xylene (BTEX). We performed aerobic microcosm studies by inoculating AFFF-impacted soil with medium containing 6:2 fluorotelomer thioether amido sulfonate (FtTAoS) and either diethyl glycol monobutyl ether (DGBE), a common AFFF ingredient, or BTEX compounds as the main carbon and energy source. BTEX-amended microcosms produced 4.3-5.3 fold more perfluoroalkyl carboxylates (PFCAs) than DGBE-amended ones, even though both organic carbon sources induced similar 6:2 FtTAoS biotransformation rates. In enrichments of AFFF-impacted solids selecting for BTEX biodegradation, we detected the presence of genes encoding toluene dioxygenase as well as larger abundances of transformation products from thioether oxidation that complement larger quantities of terminal transformation products. Our findings indicate that enrichment of BTEX-degrading microorganisms in the AFFF-impacted soil enhanced the conversion of 6:2 FtTAoS to PFCAs. These results provide insights into the high ratio of PFAAs to precursors at AFFF-impacted sites with history of BTEX bioremediation.

Background: Per- and polyfluoroalkyl substances (PFASs) are widespread and persistent environmental contaminants. Exposure to several PFASs has been associated with altered immune function in humans, including autoimmune disease and impaired response to vaccination. However, changes to the profile of inflammatory biomarkers in adults exposed to PFASs has not been extensively described., Objective: To estimate cross-sectional associations between serum PFASs and markers of inflammation among adults in a population exposed to aqueous film forming foam (AFFF)-contaminated drinking water., Methods: We quantified concentrations of 48 PFASs in non-fasting serum samples from 212 non-smoking adults. In the same serum samples, we measured concentrations of ten pro- and anti-inflammatory cytokines. We restricted analysis to seven PFASs detected in >85% of participants and the following four cytokines detected in ≥30% of participants: interleukin [IL]-1β, IL-6, IL-10, and tumor necrosis factor [TNF]-α. We fit multiple linear regression or logistic regression models, adjusted for potential confounders, to estimate associations between concentrations of each PFAS and either continuous or categorical (above vs below limit of detection) concentrations of each cytokine. We additionally applied Bayesian kernel machine regression to describe the combined effect of the PFAS mixture on each cytokine outcome., Results: Certain PFAS concentrations in this sample were elevated compared to a US nationally representative sample; median levels of PFHxS, ΣPFOS and ΣPFOA in this sample were 13.8, 2.1 and 1.7 times higher, respectively, than medians observed in the U.S., Sample: Higher concentrations of multiple PFASs were significantly associated with lower odds of detectable IL-1β. Weaker associations were observed with other cytokines. In general, perfluoroalkyl carboxylic acids had inverse associations with TNF-α, whereas the perfluoroalkyl sulfonic acids showed positive associations., Conclusions: We observed preliminary evidence of altered inflammatory profiles among adults with elevated serum concentrations of PFASs due to contaminated drinking water. Modifications to inflammatory pathways may be one mechanism by which PFAS exposures produce adverse health effects in humans, but this finding requires verification in longitudinal studies as well as phenotypic anchoring to immune function outcomes., (Copyright © 2021 Elsevier GmbH. All rights reserved.)

Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF 2 -homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

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 (CF 2 ≤ 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.

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

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.

Around the globe, on-site wastewater-treatment systems (OWTSs) are critical for rural communities without access to a municipal sewer system. However, their treatment efficiency does not match that of modern wastewater-treatment plants. The impact of OWTS discharge on nearby aquatic ecosystems and their resident fish species is poorly understood. In the present study, larval and adult fathead minnows (Pimephales promelas) and adult sunfish (Lepomis macrochirus) were exposed for 21 days to two trace organic contaminant (TOrC) mixtures replicating water chemistry derived from a previous environmental study. Larval fathead minnows were assessed for survival, growth, predator avoidance, and feeding efficiency. Adult fathead minnows and sunfish were assessed for a suite of physiological endpoints (condition indices, vitellogenin, glucose), histological changes, and fecundity. The only observed effect of TOrC mixture exposure on larval fathead minnows was a decrease in feeding efficiency. Effects were mixed in exposed adult fishes, except for male sunfish which realized a significant induction of vitellogenin (p < 0.05). The consequences of TOrC mixture exposure in the present controlled laboratory study match effects observed in wild-caught sunfish in a corresponding field study. The present study begins to bridge the gap by connecting nonpoint OWTS pollution with biological effects observed in resident lake fish species. Given the effects observed despite the brevity of the laboratory mixture exposure, longer-term studies are warranted to understand the full impacts of OWTS discharge to nearby aquatic ecosystems.  Environ Toxicol Chem 2021;40:3193-3204. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA., (© 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.)

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/m 3 for PFCAs and 14.1 kWh/m 3 for PFOS to values > 100 kWh/m 3 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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) are compounds manufactured for use in paints, cleaning agents, fire suppressants, nonstick cookware, food containers, and water-resistant products. Concerns about PFAS stem from their ubiquitous presence in the environment, persistence, and variable/uncertain bioaccumulation and toxicity. In the present study, 5 perfluoroalkyl acids and one polyfluoroalkyl substance were administered to white-footed mice (Peromyscus leucopus) to elucidate the kinetics of each chemical over 28 d of exposure. Perfluorooctanoate, perfluorohexane sulfonate (PFHxS), and perfluorobutane sulfonate were administered to male and female mice via drinking water. Perfluorooctane sulfonate, perfluorononanoate, 6:2 fluorotelomer sulfonate, and PFHxS were administered to male and female mice via oral gavage. Blood samples collected after 14 or 21 and 28 d of exposure were analyzed for individual PFAS concentrations via liquid chromatography-tandem mass spectrometry. In general, a plateau in serum concentration in this toxicity test-relevant timeline depended on interactions between 1) the type of PFAS (i.e., perfluoroalkyl sulfonic acids [PFSAs] vs perfluoroalkyl carboxylic acids [PFCAs] vs polyfluorinated), 2) continuous versus bolus dosing, and 3) to a lesser extent, sex. Specifically, PFCAs were detected at higher concentration in females than males, whereas PFSAs were generally detected at similar levels across sex. An exception occurred when PFHxS yielded higher serum levels in males than females through bolus, but not continuous, dosing. Type of PFAS had the largest impact on serum concentrations, whereas sex had the lowest. As such, future work on the toxicokinetics of PFAS in common ecological receptors would be valuable to further explore these patterns. Environ Toxicol Chem 2021;40:2886-2898. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA., (© 2021 SETAC.)

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic and 37 inorganic chemicals was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier B.V.)

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

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

POLY: and perfluorinated alkyl substances (PFASs) are ubiquitously detected all around the world. Herein, for the first time, concentrations of 16 selected legacy and emerging PFASs are reported for sediment and edible fish collected from the Saudi Arabian Red Sea. Mean concentrations varied from 0.57 to 2.6 μg kg -1 dry weight (dw) in sediment, 3.89-7.63 μg kg -1 dw in fish muscle, and 17.9-58.5 μg kg -1 dw in fish liver. Wastewater treatment plant effluents represented the main source of these compounds and contributed to the exposure of PFAS to biota. Perfluorooctane sulfonate (PFOS) was the most abundant compound in sediment and fish tissues analysed, comprising between 42 and 99% of the ∑ 16 PFAS. The short chain perfluorobutanoate (PFBA) was the second most dominant compound in sediment and was detected at a maximum concentration of 0.64 μg kg -1 dw. PFAS levels and patterns differed between tissues of investigated fish species. Across all fish species, ∑ 16 PFAS concentrations in liver were significantly higher than in muscle by a factor ranging from 3 to 7 depending on fish species and size. The PFOS replacements fluorotelomer sulfonate (6:2 FTS) and perfluorobutane sulfonate (PFBS) exhibited a bioaccumulation potential in several fish species and 6:2 FTS, was detected at a maximum concentration of 7.1 ± 3.3 μg kg -1 dw in a doublespotted queenfish (Scomberoides lysan) liver. PFBS was detected at a maximum concentration of 2.65 μg kg -1 dw in strong spine silver-biddy (Gerres longirostris) liver. The calculated dietary intake of PFOS, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorohexane sulfonic acid (PFHxS) exceeded the safety threshold established by the European Food Safety Authority (EFSA) in 2020 in doublespotted queenfish muscle, indicating a potential health risk to humans consuming this fish in Jeddah, Saudi Arabia., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: Humans are primary drivers of environmental contamination worldwide, including in drinking-water resources. In the United States (US), federal and state agencies regulate and monitor public-supply drinking water while private-supply monitoring is rare; the current lack of directly comparable information on contaminant-mixture exposures and risks between private- and public-supplies undermines tapwater (TW) consumer decision-making., Methods: We compared private- and public-supply residential point-of-use TW at Cape Cod, Massachusetts, where both supplies share the same groundwater source. TW from 10 private- and 10 public-supply homes was analyzed for 487 organic, 38 inorganic, 8 microbial indicators, and 3 in vitro bioactivities. Concentrations were compared to existing protective health-based benchmarks, and aggregated Hazard Indices (HI) of regulated and unregulated TW contaminants were calculated along with ratios of in vitro exposure-activity cutoffs., Results: Seventy organic and 28 inorganic constituents were detected in TW. Median detections were comparable, but median cumulative concentrations were substantially higher in public supply due to 6 chlorine-disinfected samples characterized by disinfection byproducts and corresponding lower heterotrophic plate counts. Public-supply applicable maximum contaminant (nitrate) and treatment action (lead and copper) levels were exceeded in private-supply TW samples only. Exceedances of health-based HI screening levels of concern were common to both TW supplies., Discussion: These Cape Cod results indicate comparable cumulative human-health concerns from contaminant exposures in private- and public-supply TW in a shared source-water setting. Importantly, although this study's analytical coverage exceeds that currently feasible for water purveyors or homeowners, it nevertheless is a substantial underestimation of the full breadth of contaminant mixtures documented in the environment and potentially present in drinking water., Conclusion: Regardless of the supply, increased public engagement in source-water protection and drinking-water treatment, including consumer point-of-use treatment, is warranted to reduce risks associated with long-term TW contaminant exposures, especially in vulnerable populations., (Published by Elsevier Ltd.)

Understanding how exposure to aqueous film-forming foam (AFFF)-impacted drinking water translates to bioaccumulation of per- and polyfluoroalkyl substances (PFASs) is essential to assess health risks. To investigate spatial variability of PFAS exposure in communities near an AFFF source zone, blood serum was collected in 2018 from 220 adult residents of El Paso County (Colorado), as were raw water samples from several wells. C6 and C8 perfluoroalkyl sulfonates (PFSAs) were predominant in serum and water. PFASs were most elevated in the water district nearest the source zone (median ∑PFSA of 618 ng/L in water and 33 ng/mL in serum). A novel PFAS, unsaturated perfluorooctane sulfonate, was detected in >80% of water and serum samples at low concentrations (≤1.9 ng/mL in serum). Drinking water wells nearest the source zone displayed increased prevalence of perfluoroalkyl sulfonamide precursors not detected in serum. Serum-to-water ratios were the greatest for long-chain PFASs and were elevated in the least impacted water district. Additional serum samples collected from a subset of study participants in June 2019 showed that PFAS concentrations in serum declined after exposure ceased, although declines for perfluoropentane sulfonate were minimal. Our findings demonstrate that AFFF-impacted communities are exposed to complex, spatially variable mixtures of PFASs.

The source tracking of per- and polyfluoroalkyl substances (PFASs) is a new and increasingly necessary subfield within environmental forensics. We define PFAS source tracking as the accurate characterization and differentiation of multiple sources contributing to PFAS contamination in the environment. PFAS source tracking should employ analytical measurements, multivariate analyses, and an understanding of PFAS fate and transport within the framework of a conceptual site model. Converging lines of evidence used to differentiate PFAS sources include: identification of PFASs strongly associated with unique sources; the ratios of PFAS homologues, classes, and isomers at a contaminated site; and a site's hydrogeochemical conditions. As the field of PFAS source tracking progresses, the development of new PFAS analytical standards and the wider availability of high-resolution mass spectral data will enhance currently available analytical capabilities. In addition, multivariate computational tools, including unsupervised (i.e., exploratory) and supervised (i.e., predictive) machine learning techniques, may lead to novel insights that define a targeted list of PFASs that will be useful for environmental PFAS source tracking. In this Perspective, we identify the current tools available and principal developments necessary to enable greater confidence in environmental source tracking to identify and apportion PFAS sources.

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

The widespread use of aqueous film-forming foam (AFFF) for firefighting activities (e.g., fire training to extinguish fuel-based fires at aircraft facilities) has led to extensive groundwater and soil contamination by per- and polyfluoroalkyl substances (PFASs) that are highly recalcitrant to destruction using conventional treatment technologies. This study reports on the hydrothermal alkaline treatment of diverse PFASs present in AFFFs. Quantitative and semiquantitative high-resolution mass spectrometry analyses of PFASs demonstrate a rapid degradation of all 109 PFASs identified in two AFFFs (sulfonate- and fluorotelomer-based formulations) in water amended with an alkali (e.g., 1-5 M NaOH) at near-critical temperature and pressure (350 °C, 16.5 MPa). This includes per- and polyfluoroalkyl acids and a range of acid precursors. Most PFASs were degraded to nondetectable levels within 15 min, and the most recalcitrant perfluoroalkyl sulfonates were degraded within 30 min when treated with 5 M NaOH. 19 F NMR spectroscopic analysis and fluoride ion analysis confirm the near-complete defluorination of PFASs in both dilute and concentrated AFFF mixtures, and no stable volatile organofluorine species were detected in reactor headspace gases by the gas chromatography-mass spectrometry analysis. These findings indicate a significant potential for application of hydrothermal treatment technologies to manage PFAS waste streams, including on-site treatment of unused AFFF chemical stockpiles, investigation-derived wastes, and concentrated source zone materials.

Per and polyfluoroalkyl substances (PFASs) are an important class of organic pollutants. Many diverse PFASs are used in commerce and most are not amenable to conventional targeted chemical analysis due to lack of reference standards. Therefore, methods for elucidating the chemical structure of previously unreported or unexpected PFASs in the environment rely extensively on high-resolution mass spectrometry (HRMS). High-throughput structure identification by HRMS is hindered by a lack of PFAS molecular databases and tandem mass spectral libraries. Here, we report a new approach for generating an environmentally relevant PFAS molecular database constructed from curated structure lists and biotic/abiotic in silico predicted transformation products. Further, we have generated a predicted tandem mass spectral library using computational mass spectrometry tools. Results demonstrate the utility of the generated database and approach for identifying PFASs in HRMS-enabled suspect- and nontarget screening studies.

Soil and groundwater from an aqueous film-forming foam (AFFF)-impacted site were sampled at high resolution ( n = 105 for soil, n = 58 for groundwater) and analyzed for an extensive list of anionic, zwitterionic, and cationic poly- and perfluoroalkyl substances (PFASs). Spatial trends for perfluoroalkyl acids and many precursors enabled a better understanding of PFAS composition, transport, and transformation. All PFASs without analytical standards were semi-quantified. Summed PFAS and individual PFAS concentrations were often higher at depth than near the surface in soil and groundwater. Zwitterionic and cationic compounds composed a majority of the total PFAS mass (up to 97%) in firefighter training area (FTA) soil. Composition of PFAS class, chain length, and structural isomers changed with depth and distance from the FTA, suggesting in situ transformation and differential transport. The percentage of branched perfluorooctane sulfonate increased with depth, consistent with differential isomeric transport. However, linear perfluorooctanoic acid (PFOA) was enriched, suggesting fluorotelomer precursor transformation to linear PFOA. Perfluorohexane sulfonamide, a potential transformation product of sulfonamide-based PFASs, was present at high concentrations (maximum 448 ng/g in soil, 3.4 mg/L in groundwater). Precursor compounds may create long-term sources of perfluoroalkyl acids, although many pathways remain unknown; precursor analysis is critical for PFAS fate and transport understanding.

Per- and polyfluoroalkyl substances (PFASs) are today considered important constituents of the continuously growing substance group of persistent contaminants of emerging environmental concern (PCEC). Here, we report for the first time the concentrations of 12 relevant PFASs in 28 marine water samples from the Saudi Arabian coastal waters of the Red Sea. The sum levels of 12 PFASs (Σ 12 PFAS) in surface seawater ranged from -1 . For the reference background site of this study, Σ 12 PFAS levels ranged from

The aim of this study was to assess the soil-water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil-water partitioning coefficients (log  K d values) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol ( R 2 = 0.94, p < 0.0001). Across all soils, the K d values of all short-chain PFASs (≤5 -CF2- moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5  log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The K d values of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

Transport of poly- and perfluoroalkyl substances (PFAS) at aqueous film-forming foam (AFFF)-impacted sites is limited by various processes that can retain PFAS mass within the source area. This study used concentration data obtained via a high-resolution sampling and analytical protocol to estimate the PFAS mass distribution in source and downgradient areas of a former firefighter training area. The total PFAS mass present at the site was approximately 222 kg, with 106 kg as perfluoroalkyl acids (PFAAs) and 116 kg as polyfluorinated precursors. Zwitterionic and cationic PFAS represented 83% of the total precursor mass and were found primarily in the source and up/side-gradient areas (75%), likely due to preferential hydrophobic partitioning, electrostatic interactions, and diffusion into lower-permeability soils. Based on the release history and the high percentage of total PFAS mass represented by precursors (primarily electrochemical fluorination-derived compounds), the estimated conversion rate of precursors to PFAAs was less than 2% annually. Eighty-two percent of the total PFAS mass was encountered in lower-permeability soils, which limited the potential for advection and transformation. This contributed to a 99% decrease in the mass discharge rate at the far-downgradient plume (0.048 kg/yr compared to the near-source area (3.6 kg/yr)). The results provide field-scale evidence of the importance of these PFAS retention processes at sites where AFFF has been released.

Irrigation water or soil contaminated with per- and polyfluoroalkyl substances (PFASs) raises concerns among regulators tasked with protecting human health from potential PFAS-contaminated food crops, with several studies identifying crop uptake as an important exposure pathway. We estimated daily dietary exposure intake of individual PFASs in vegetables for children and adults using Monte Carlo simulation in a tiered stochastic modeling approach: exposures were the highest for young children (1-2 years > adults > 3-5 years > 6-11 years > 12-19 years). Using the lowest available human health toxicity reference values (RfDs) and no additional exposure, estimated fifth percentile risk-based threshold concentrations in irrigation water were 38 ng/L (median 180 ng/L) for perfluorooctanoate (PFOA) and 140 ng/L (median 850 ng/L) for perfluorooctane sulfonate (PFOS). Thus, consumption of vegetables irrigated with PFAS-impacted water that meets the current 70 ng/L of PFOA and PFOS U.S. Environmental Protection Agency's lifetime health advisory for drinking water may or may not be protective of vegetable exposures to these contaminants. Hazard analyses using real-world PFAS-contaminated groundwater data for a hypothetical farm showed estimated exposures to most PFASs exceeding available or derived RfDs, indicating water-to-crop transfer is an important exposure pathway for communities with PFAS-impacted irrigation water.

Aqueous film-forming foams (AFFFs) are complex per- and polyfluoroalkyl substance (PFAS)-containing mixtures used extensively as fire suppressants. AFFF-impacted groundwater and surface water have contaminated drinking water with PFASs in many communities, raising concerns about health effects from drinking water exposures. As individual PFASs have been identified as immune hazards, the immunotoxicity of complex PFAS mixtures is also a concern. Adult female and male C57BL/6 mice were given a commercial AFFF formulation for 10 days via gavage; administered dose was based on combined content of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) measured in the formulation (0, 1.88, 3.75, 7.5, or 10 mg PFOS+PFOA/kg body weight). A PFOA positive control of 7.5 mg/kg body weight was also given. Compared with the 0 mg/kg group, the following changes were noted: Body weights of males exposed to 7.5 and 10 mg PFOS+PFOA/kg were reduced by 15%, on average; female body weights did not differ. Average relative liver weights were increased 50%-200% in males and 37.5%-193% in females and liver peroxisome proliferation was increased 2- to 12-fold in all doses of both sexes. Antigen-specific antibody production was suppressed, on average, by 13% in males and by 12.4% in females across all doses. Spleen cellularity and lymphocyte subpopulations did not differ by dose for either sex. Our data indicate that though this complex PFAS mixture contained fairly low PFOA content, it induced changes in C57BL/6 mice similar to changes induced by PFOA alone, likely due to the presence of PFOS and many other PFASs., (© The Author(s) 2020. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Transport of ten perfluoroalkyl acids (PFAAs) was studied with one-dimensional (1-D) saturated column experiments using four soil types with an organic carbon fraction (f oc ) range of ~0-0.045. Columns were operated under conditions relevant to aqueous film-forming foam (AFFF)-impacted fire protection training areas to determine the ability of equilibrium transport parameters to describe 1-D PFAA transport, if rate-limited sorption influences PFAA transport, and if kinetic parameters can be used to evaluate factors causing rate-limited sorption. Results of initial screening of PFAA breakthrough found that over half of the breakthrough curves deviated from equilibrium transport and merited further investigation. Subsequent analysis showed that, in many cases, these deviations could be accounted for by considering the range of applicable equilibrium K d values (i.e. based on standard deviation) applicable to the solid phase. Thus, transport of the majority of PFAAs in 3 soils with f oc of 0-0.017 was not impacted by rate-limited sorption. Further, low sorption led to transport that was essentially simultaneous for the majority of PFAAs in these porous media. Exceptions were observed for long-chain PFAAs, and also in a fourth soil with f oc of 0.045, which indicated the potential for rate-limited sorption to impact transport in some scenarios. Subsequent flow interruption experiments isolating kinetic behavior confirmed rate-limited sorption caused nonequilibrium transport. Linear free energy relationships (LFERs) developed in previous work to predict the inverse relationship between mass transfer coefficients (k) and sorption parameters (i.e., K d ) were used to estimate values of k for PFAAs in this study. Resulting k values were 10 -3 to 10 -8  h -1 , consistent with previously measured kinetic parameters for other polar and anionic compounds. Models incorporating estimated k values resulted in improved predictions of breakthrough observed in nonequilibrium scenarios (R 2 0.83-0.98), but k values will require further validation prior to broader application. This work illustrates rate-limited sorption considerations are needed to describe 1-D column saturated transport for some PFAAs and solid phases. At field scales, subsurface heterogeneity and PFAA precursor transformation may be equally or even more important in determining saturated PFAA transport, but kinetic parameters in this study may help to determine relative contributions of rate-limited sorption to overall transport., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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

Per- and polyfluoroalkyl substances (PFASs) are widespread in the blood of the general human population, and their bioaccumulation is of considerable scientific and regulatory interest. PFAS exposure resulting from aqueous film-forming foam (AFFF) ingestion is poorly understood due to the complexity of AFFF mixtures and the presence of polyfluorinated substances that may undergo metabolic transformation. C57BL/6 mice were dosed with an AFFF primarily containing electrochemically fluorinated PFASs for 10 days, followed by a 6 day depuration. Urine was collected throughout the study and serum was collected post-depuration. Samples were analyzed via high-resolution mass spectrometry. Relative to the dosing solution, C6 and C7 perfluoroalkyl sulfonates (PFSAs) were enriched in dosed mouse serum, suggesting in vivo transformation of sulfonamide precursors. Some substituted C8 PFSAs [keto-perfluorooctane sulfonate (PFOS), hydrogen-PFOS, and unsaturated PFOS] appeared to be more bioaccumulative than linear PFOS, or were formed in vivo from unidentified precursors. A series of seven peaks in dosed mouse serum was tentatively identified as sulfonimide dimers that were either a minor component of the AFFF or were formed via metabolism of other AFFF components. This work highlights the importance of sulfonamide precursors in contributing to bioaccumulation of AFFF-associated PFSAs and identifies several classes of potentially bioaccumulative novel PFASs that warrant further investigation.