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Per- and poly-fluoroalkyl substances (PFASs) are contaminants of emerging concern, yet the understanding of factors that control their leaching and release from contaminated soils remains limited. This study aimed to investigate the impact of dissolved organic carbon (DOC) on the release of PFASs-specifically, perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA)from soils contaminated by aqueous film forming foam (AFFF). Batch aqueous leaching experiments were conducted on AFFF-contaminated soils under alkaline solution conditions (pH 9.5, 10.5, and 12) as it enhances leaching of both PFAS and DOC. Leaching of PFOS was significantly increased under alkaline conditions. Although the leaching of PFAS generally increased with pH, PFOS appeared to be more retained under the very alkaline pH conditions used in this study. At the same solution pH, leaching of PFOS and DOC was less in Ca(OH) 2 than in NaOH. The retention of PFOS under these conditions may be attributable to the shielding of the negative charge of the soil components and colloids (e.g., DOC and clay minerals) in the leachates and/or the screening of negative charges on head groups of PFOS due to the high concentration of divalent cations. Solution chemistry affected desorption of PFOS more than PFHxS and PFOA. The study highlights that the influence of DOC on PFAS leaching and transport can be very complex, and depends on leachate chemistry (e.g., pH and cation type), PFAS chemistry, the magnitude of PFAS contamination and factors that influence the solid:liquid partitioning of organic carbon in soil., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Shervin Kabiri reports financial support was provided by Australian Research Council. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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.)

Per- and polyfluoroalkyl substances (PFAS) receive global attention due to their adverse effects on human health and the environment. Fish consumption is a major source of human PFAS exposure. The aim of this work was to address the lack of harmonization within legislations (in the EU and the USA) and highlight the level of PFAS in fish exposed to pollution from diffuse sources in the context of current safety thresholds. A non-exhaustive literature review was carried out to obtain PFAS concentrations in wild fish from the Norwegian mainland, Svalbard, the Netherlands, the USA, as well as sea regions (North Sea, English Channel, Atlantic Ocean), and farmed fish on the Dutch market. Median sum wet weight concentrations of PFOA, PFNA, PFHxS, and PFOS ranged between 0.1 µg kg -1 (farmed fish) and 22 µg kg -1 (Netherlands eel). Most concentrations fell below the EU environmental quality standard (EQS biota ) for PFOS (9.1 µg kg -1 ) and would not be defined as polluted in the EU. However, using recent tolerable intake or reference dose values in the EU and the USA revealed that even limited fish consumption would lead to exceedance of these thresholds - possibly posing a challenge for risk communication., Competing Interests: Declaration of competing interest Christopher P. Higgins is involved in various PFAS litigation activities. The other 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.)

Though long recognized as synthetic precursors to other poly- and perfluoroalkyl substances (PFASs), most poly- and perfluoroalkyl sulfonyl halides (PASXs) cannot be directly measured and have generally received minimal attention. Inspired by the redox reaction between sulfonyl halide groups and p -toluenethiol in organic chemistry, we developed a novel nontarget analysis strategy for PASXs by intergrating derivatization and specific fragment-based liquid chromatography-high resolution mass spectrometry screening for m / z 82.961 [SO 2 F - ] and m / z 95.934 [S 2 O 2 - ]. By using this strategy, we discovered 11 PASXs, namely, perfluoroalkyl sulfonyl fluorides (5), polyfluoroalkyl sulfonyl fluorides (2), unsaturated perfluoroalkyl sulfonyl fluoride (1), and perfluoroalkyl sulfonyl chlorides (3) in soil samples collected from an abandoned fluorochemical manufacturing park. These average ∑PASXs concentrations were 1120 μg kg -1 (range: 9.7-9860 μg kg -1 ), which were very likely to be the key intermediates and undesired byproducts of electrochemical fluorination processes. Spatial variation in the mass ratio of ∑PASXs to ∑PFSAs (range: 0.7-795%) also indicates their different transportation pathways. More importantly, the decline of PASXs and increase of perfluoroalkyl sulfonates (when compared to a prior study at this site) suggest the continued hydrolysis of PASXs and the relatively fast environmental transformation rates in the abandoned fluorochemical park soils. Overall, these findings demonstrated the utility of a novel nontarget analysis strategy, which may change most PASXs from inferred precursors to measured intermediates and further could be adapted for structures, distribution, and transformation studies of PFASXs in other matrices.

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.

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

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

We report numerical simulations of surface gravity waves forced at small scale and the subsequent inverse cascade of wave action. We combine the spectral approach to simulating weakly nonlinear waves with the capabilities of modern graphics processing units to reach unprecedented scale separation between the forcing and domain scales. The resulting broad inertial range allows for an unambiguous confirmation of the theoretical prediction for the spectrum in the inverse cascade regime, both in terms of spectral index and dependence of the spectral level on the action flux.

The widespread use of aqueous film-forming foam (AFFF) for firefighting and firefighter training has led to extensive per- and polyfluoroalkyl substance (PFAS) contamination in the environment. Challenges remain in the analytical determination of PFASs via liquid chromatography-mass spectrometry (LC-MS), particularly when attempting to include ultrashort-chain perfluoroalkyl acids (PFAAs) and longer-chain anionic and zwitterionic PFASs in a single direct injection. In this study, we assessed the performance of three analytical LC columns (C18, JJ, and Acclaim columns) to separate targeted and suspect PFASs in AFFF-impacted water samples collected from five sites. The C18 column failed to retain ultrashort-chain PFAAs while the JJ and Acclaim columns were not suitable for hydrophobic PFASs. Ultrashort-chain PFAAs were detected at three sites and comprised 1.6-18% of the total perfluoroalkyl carboxylic and sulfonic acids. Semi-quantified concentrations of suspect PFASs comprised 0.70-13% of the total PFASs. When attempting to capture the entirety of the PFAS mass in a water sample, the C18 column captured the broadest suite of suspect PFASs, while the JJ column quantified the most total PFAS mass. Results of this study highlight the importance and tradeoffs of LC column choice to comprehensively determine the composition of PFASs and their concentrations in AFFF-impacted water samples., 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 Elsevier B.V. All rights reserved.)

Only a fraction of the total number of per- and polyfluoroalkyl substances (PFAS) are monitored on a routine basis using targeted chemical analyses. We report on an approach toward identifying bioactive substances in environmental samples using effect-directed analysis by combining toxicity testing, targeted chemical analyses, and suspect screening. PFAS compete with the thyroid hormone thyroxin (T 4 ) for binding to its distributor protein transthyretin (TTR). Therefore, a TTR-binding bioassay was used to prioritize unknown features for chemical identification in a PFAS-contaminated sediment sample collected downstream of a factory producing PFAS-coated paper. First, the TTR-binding potencies of 31 analytical PFAS standards were determined. Potencies varied between PFAS depending on carbon chain length, functional group, and, for precursors to perfluoroalkyl sulfonic acids (PFSA), the size or number of atoms in the group(s) attached to the nitrogen. The most potent PFAS were the seven- and eight-carbon PFSA, perfluoroheptane sulfonic acid (PFHpS) and perfluorooctane sulfonic acid (PFOS), and the eight-carbon perfluoroalkyl carboxylic acid (PFCA), perfluorooctanoic acid (PFOA), which showed approximately four- and five-times weaker potencies, respectively, compared with the native ligand T 4 . For some of the other PFAS tested, TTR-binding potencies were weak or not observed at all. For the environmental sediment sample, not all of the bioactivity observed in the TTR-binding assay could be assigned to the PFAS quantified using targeted chemical analyses. Therefore, suspect screening was applied to the retention times corresponding to observed TTR binding, and five candidates were identified. Targeted analyses showed that the sediment was dominated by the di-substituted phosphate ester of N-ethyl perfluorooctane sulfonamido ethanol (SAmPAP diester), whereas it was not bioactive in the assay. SAmPAP diester has the potential for (bio)transformation into smaller PFAS, including PFOS. Therefore, when it comes to TTR binding, the hazard associated with this substance is likely through (bio)transformation into more potent transformation products. Environ Toxicol Chem 2024;43:245-258. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

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.

Improved stormwater treatment is needed to prevent toxic and mobile contaminant transport into receiving waters and allow beneficial use of stormwater runoff. In particular, safe capture of stormwater runoff to augment drinking water supplies is contingent upon removing dissolved trace organic contaminants (TrOCs) not captured by conventional stormwater control measures. This study builds upon a prior laboratory-based column study investigating biochar and regenerated activated carbon (RAC) amendment for removing hydrophilic trace organic contaminants (HiTrOCs) and poly- and perfluoroalkyl substances (PFASs) from stormwater runoff. A robust contaminant transport model framework incorporating time-dependent flow and influent concentration is developed and validated to predict HiTrOC and PFAS transport in biochar- and RAC-amended stormwater filters. Specifically, parameters fit using a sorption-retarded intraparticle pore diffusion transport model were validated using data further along the depth of the column and compared to equilibrium batch isotherms. The transport model and fitted parameters were then used to estimate the lifetime of a hypothetical stormwater filter in Seal Beach, CA, to be 35 ± 6 years for biochar- and 51 ± 17 years for RAC-amended filters, under ideal conditions with no filter clogging. This work offers insights on the kinetics of HiTrOC and PFAS transport within biochar and RAC filters and on the impact of filter design on contaminant removal performance and longevity.

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.

Effective monitoring tools, including passive samplers, are essential for the wide range of per- and polyfluoroalkyl substances (PFASs) in aquatic matrices. However, knowledge of the extent and mechanisms of PFASs sorption with sorbents in a passive sampling context is limited. To address this, sorption behavior of 45 anionic, neutral and zwitterionic PFASs ranging in perfluorocarbon chain length (C 3 -C 16 ) and functional groups with 11 different commercial sorbents (cross-linked β-cyclodextrin polymers, activated carbon, anion exchange (AE), cation exchange, hydrophilic-lipophilic balanced (HLB) and non-polar) was investigated. A broad range of equilibrium sorbent-MilliQ water (MQ) distribution coefficients (K d ) were observed (10 -1.95 to 10 8.30 mL g -1 ). Similar sorbent types (e.g., various AE and HLB sorbents) exhibited very different sorption behavior, likely due to their different polymeric structures and relative importance of sorbate/sorbent interactions other than coulombic interactions. HLB and AE with hydroxyl functionalities are most effective for sampling of the full suite of PFASs. Reduced sorptive affinity was observed in the presence of matrix co-constituents in wastewater influent for most PFASs. HLB had the smallest reduction in log K d in wastewater suggesting that these sorbents are appropriate for applications in complex matrices. Sufficient sorbent capacity was observed for linear uptake of many target analytes which facilitates passive sampling., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Removal of per- and polyfluoroalkyl substances (PFASs) from water or their immobilization in soil using carbon-based sorbents is one of the cost-effective techniques. Considering the variety of carbon-based sorbents, identifying the key sorbent properties responsible for PFASs removal from solution or immobilization in the soil can assist in the selection of the best sorbents for management of contaminated sites. This study evaluated the performance of 28 carbon-based sorbents including granular and powdered activated carbon (GAC and PAC), mixed mode carbon mineral material, biochars, and graphene-based materials (GNBs). The sorbents were characterized for a range of physical and chemical properties. PFASs' sorption from an AFFF-spiked solution was examined via a batch experiment, while their ability to immobilize PFASs in soil was tested following mixing, incubation and extraction using the Australian Standard Leaching Procedure. Both soil and solution were treated with 1 % w/w sorbents. Comparing different carbon-based materials, PAC, mixed mode carbon mineral material and GAC were the most effective in sorbing PFASs in both solution and soil. Among the different physical characteristics measured, the sorption of long-chain and more hydrophobic PFASs in both soil and solution was best correlated with sorbent surface area measured using methylene blue, which highlights the importance of mesopores in PFASs sorption. Iodine number was found to be a better indicator of the sorption of short-chain and more hydrophilic PFASs from solution but was found to be poorly correlated with PFASs immobilization in soil for activated carbons. Sorbents with a net positive charge performed better than those with a net negative charge, or no net charge. This study showed that surface area measured by methylene blue and surface charge are the best indicators of sorbent performance with respect to sorption/reducing leaching of PFASs. These properties may be helpful in selecting sorbents for PFASs remediation of soils/waters., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Shervin kabiri reports financial support was provided by The University of Adelaide School of Agriculture Food & Wine. Shervin kabiri reports a relationship with The University of Adelaide School of Agriculture Food & Wine that includes: funding grants., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Public transport disruptions caused by the COVID-19 pandemic had wide-ranging impacts on the ability of individuals to access health care. Individuals with opioid use disorder represent an especially vulnerable population due to the necessity of frequent, supervised doses of opioid agonists. Focused on Toronto, a major Canadian city suffering from the opioid epidemic, this analysis uses novel realistic routing methodologies to quantify how travel times to individuals\220 nearest clinics changed due to public transport disruptions from 2019 to 2020. Individuals seeking opioid agonist treatment face very constrained windows of access due to the need to manage work and other essential activities. We find that thousands of households in the most materially and socially deprived neighbourhoods crossed 30 and 20-minute travel time thresholds to their nearest clinic. As even small changes to travel times can lead to missed appointments and heighten the chances of overdose and death, understanding the distribution of those most impacted can help inform future policy measures to ensure adequate access to care., Competing Interests: Declarations of Interest None., (Copyright © 2023 Elsevier B.V. All rights reserved.)

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.

A remote sampling approach was developed at Eurofins for quantifying per- and polyfluoroalkyl substances (PFASs) in whole blood samples collected using volumetric absorptive microsamplers (VAMSs), which allow for self-collection of blood using a finger prick. This study compares PFAS exposure measured by self-collection of blood using VAMSs to the standard venous serum approach. Blood samples were collected from participants ( n = 53) in a community with prior PFAS drinking water contamination using a venous blood draw as well as participant self-collection using VAMSs. Whole blood from the venous tubes was also loaded onto VAMSs to compare differences in capillary vs venous whole blood PFAS levels. Samples were quantified for PFASs using liquid chromatography tandem mass spectrometry and online solid-phase extraction. PFAS levels in serum were highly correlated with measurements in capillary VAMSs ( r ≥ 0.91 and p < 0.05). Serum PFAS levels were generally twofold higher than whole blood, reflecting expected differences in their composition. Of interest, FOSA was detected in whole blood (both venous and capillary VAMSs) but not in serum. Overall, these findings indicate that VAMSs are useful self-collection tools for assessing elevated human exposure to PFASs.

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.

One of the most common cell shape changes driving morphogenesis in diverse animals is the constriction of the apical cell surface. Apical constriction depends on contraction of an actomyosin network in the apical cell cortex, but such actomyosin networks have been shown to undergo continual, conveyor belt-like contractions before the shrinking of an apical surface begins. This finding suggests that apical constriction is not necessarily triggered by the contraction of actomyosin networks, but rather can be triggered by unidentified, temporally-regulated mechanical links between actomyosin and junctions. Here, we used C. elegans gastrulation as a model to seek genes that contribute to such dynamic linkage. We found that α-catenin and β-catenin initially failed to move centripetally with contracting cortical actomyosin networks, suggesting that linkage is regulated between intact cadherin-catenin complexes and actomyosin. We used proteomic and transcriptomic approaches to identify new players, including the candidate linkers AFD-1/afadin and ZYX-1/zyxin, as contributing to C. elegans gastrulation. We found that ZYX-1/zyxin is among a family of LIM domain proteins that have transcripts that become enriched in multiple cells just before they undergo apical constriction. We developed a semi-automated image analysis tool and used it to find that ZYX-1/zyxin contributes to cell-cell junctions' centripetal movement in concert with contracting actomyosin networks. These results identify several new genes that contribute to C. elegans gastrulation, and they identify zyxin as a key protein important for actomyosin networks to effectively pull cell-cell junctions inward during apical constriction. The transcriptional upregulation of ZYX-1/zyxin in specific cells in C. elegans points to one way that developmental patterning spatiotemporally regulates cell biological mechanisms in vivo. Because zyxin and related proteins contribute to membrane-cytoskeleton linkage in other systems, we anticipate that its roles in regulating apical constriction in this manner may be conserved., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Slabodnick et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

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.

Accessibility indicators are widely used in transportation, urban and healthcare planning, among many other applications. These measures are weighted sums of reachable opportunities from a given origin, conditional on the cost of movement, and are estimates of the potential for spatial interaction. Over time, various proposals have been forwarded to improve their interpretability: one of those methodological additions have been the introduction of competition. In this paper we focus on competition, but first demonstrate how a widely used measure of accessibility with congestion fails to properly match the opportunity-seeking population. We then propose an alternative formulation of accessibility with competition, a measure we call spatial availability. This measure relies on proportional allocation balancing factors (friction of distance and population competition) that are equivalent to imposing a single constraint on conventional gravity-based accessibility. In other words, the proportional allocation of opportunities results in a spatially available opportunities value which is assigned to each origin that, when all origin values are summed, equals the total number of opportunities in the region. We also demonstrate how Two-Stage Floating Catchment Area (2SFCA) methods are equivalent to spatial availability and can be reconceptualized as singly-constrained accessibility. To illustrate the application of spatial availability and compare it to other relevant measures, we use data from the 2016 Transportation Tomorrow Survey of the Greater Golden Horseshoe area in southern Ontario, Canada. Spatial availability is an important contribution since it clarifies the interpretation of accessibility with competition and paves the way for future applications in equity analysis (e.g., spatial mismatch, opportunity benchmarking, policy intervention scenario analysis)., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Soukhov et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

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.

Urban stormwater runoff is a significant driver of surface water quality impairment. Recently, attention has been drawn to potential beneficial use of urban stormwater runoff, including augmenting drinking water supply in water-stressed areas. However, beneficial use relies on improved treatment of stormwater runoff to remove mobile dissolved metals and trace organic contaminants (TrOCs). This study assesses six engineered media mixtures consisting of sand, zeolite, high-temperature gasification biochar, and regenerated activated carbon (RAC) for removing a suite of co-contaminants comprising five metals, three herbicides, four pesticides, a corrosion inhibitor, six per- and polyfluoroalkyl substances (PFASs), five polychlorinated biphenyls (PCBs), and six polycyclic aromatic hydrocarbons (PAHs). This long-term laboratory-scale column study uses a novel approach to generate reproducible synthetic stormwater that incorporates catch basin material and straw-derived dissolved organic carbon. Higher flow conditions (20 cm hr -1 ), larger sized media (0.42-1.68 mm), and downflow configuration with outlet control increase the relevance of this study to better enable implementation in the field. Biochar- and RAC-amended engineered media filters removed nearly all of the TrOCs in the effluent over the course of three months of continuous flow (480 empty bed volumes), while sample ports spaced at 25% and 50% along the column depth provide windows to observe contaminant transport. Biochar provided greater benefit to TrOC removal than RAC on a mass basis. This study used relatively high concentrations of contaminants and low biochar and RAC content to observe contaminant transport. Performance in the field is likely to be significantly better with higher biochar- and RAC-content filters and lower ambient stormwater contaminant concentrations. This study provides proof-of-concept for biochar- and RAC-amended engineered media filters operated at a flow rate of 20 cm hr -1 for removing dissolved TrOCs and metals and offers insights on the performance of biochar and RAC for improved stormwater treatment and field trials., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The reuse of oilfield produced water (PW) for agricultural irrigation has received increased attention for utility in drought-stricken regions. It was recently demonstrated that PW irrigation can affect physiological processes in food crops. However, metabolomic evaluations are important to further discern specific mechanisms of how PW may contribute as a plant-environmental stressor. Herein, the primary metabolic responses of wheat irrigated with PW and matching salinity controls were investigated. Non-targeted gas chromatography mass spectrometry (GC-MS) metabolomics was combined with multivariate analysis and revealed that PW irrigation altered the primary metabolic profiles of both wheat leaf and grain. Over 600 compounds (183 annotated metabolites) were detected that varied between controls (salinity control and tap water) and PW irrigated plants. While some of these changed metabolites are related to salinity stress, over half were found to be unique to PW. The primary metabolites exhibiting changes in abundance in leaf and grain tissues were amines/amino acids, organic acids, and saccharides. Metabolite pathway analysis revealed that amino acid metabolism, sugar metabolism, and nitrogen remobilization are all impacted by PW irrigation, independent of regular plant responses to salinity stress. These data, when combined with prior physiological studies, support a multi-faceted, physio-metabolic response of wheat to the unique stressor imposed by irrigation with PW., (Copyright © 2022 Elsevier Inc. All rights reserved.)

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

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) are important environmental contaminants, yet relatively few analytical reference standards exist for this class. Nontarget analyses performed by means of high-resolution mass spectrometry (HRMS) are increasingly common for the discovery and identification of PFASs in environmental and biological samples. The certainty of PFAS identifications made via HRMS must be communicated through a reliable and harmonized approach. Here, we present a confidence scale along with identification criteria specific to suspect or nontarget analysis of PFASs by means of nontarget HRMS. Confidence levels range from level 1a-"Confirmed by Reference Standard," and level 1b-"Indistinguishable from Reference Standard," to level 5-"Exact Masses of Interest," which are identified by suspect screening or data filtering, two common forms of feature prioritization. This confidence scale is consistent with general criteria for communicating confidence in the identification of small organic molecules by HRMS (e.g., through a match to analytical reference standards, library MS/MS, and/or retention times) but incorporates the specific conventions and tools used in PFAS classification and analysis (e.g., detection of homologous series and specific ranges of mass defects). Our scale clarifies the level of certainty in PFAS identification and, in doing so, facilitates more efficient identification., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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.)

Omega-3 polyunsaturated fatty acids (n-3 PUFAs), obtained from diet and dietary supplements, have been tested in clinical trials for the prevention or treatment of several diseases. n-3 PUFAs exert their effects by activation of free fatty acid (FFA) receptors. FFA1 receptor, expressed in the pancreas and brain, is activated by medium- to long-chain fatty acids. Despite some beneficial effects on cognition, the effects of n-3 PUFAs on the blood-brain barrier (BBB) are not clearly understood. We examined the effects of FFA1 activation on BBB permeability in vitro, using rat brain microvascular endothelial cells (RBMVEC), and in vivo, by assessing Evans Blue extravasation and by performing live imaging of brain microcirculation in adult rats. AMG837, a synthetic FFA1 agonist, produced a dose-dependent decrease in RBMVEC monolayer resistance assessed with Electric Cell-Substrate Impedance Sensing (ECIS); the effect was attenuated by the FFA1 antagonist, GW1100. Immunofluorescence studies revealed that AMG837 produced a disruption in tight and adherens junction proteins. AMG837 increased Evans Blue content in the rat brain in a dose-dependent manner. Live imaging studies of rat brain microcirculation with miniaturized fluorescence microscopy (miniscope) showed that AMG837 increased extravasation of sodium fluorescein. Taken together, our results demonstrate that FFA1 receptor activation reduced RBMVEC barrier function and produced a transient increase in BBB permeability.

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.

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

In this paper we analyze the changes in accessibility to emergency and community food services before and during the COVID-19 pandemic in the City of Hamilton, Ontario. Many of these food services are the last line of support for households facing food insecurity; as such, their relevance cannot be ignored in the midst of the economic upheaval caused by the pandemic. Our analysis is based on the application of balanced floating catchment areas and concentrates on households with lower incomes (