Use Of Aqueous Film-forming Foam Research Articles

Making waves: The progress of management strategies for cleaning and rinsing of PFAS-impacted fire suppression systems

Aircraft rescue firefighting (ARFF) vehicles often contain residual levels of per- and polyfluoroalkyl substances (PFAS) due to the global use of legacy and current use of aqueous film-forming foam (AFFF) for class B firefighting. However, numerous countries are transitioning to fluorine-free foam (F3) alternatives. There is, thus, an urgent need to develop efficient methods to rinse and clean interior ARFF surfaces thereby avoiding expensive replacement costs and preventing further discharge of PFAS to the environment. However, the unique self-assembly behavior of amphiphilic PFAS is a complicating factor that can result in measurable levels of PFAS within replacement F3 following cleanout efforts (i.e., the rebound effect). This Making Waves article aims to elucidate the emerging challenges associated with cleanout of impacted ARFF vehicles and introduce the current efforts for PFAS management of rinsate derived from cleanout of impacted fire suppression infrastructure.

Determination of Toxicity at Different Trophic Levels of Aqueous Film-Forming Foams (AFFF) Used in Fire Fighting.

Aqueous film-forming foams (AFFF), containing perfluorinated surfactants, can reach the environment. The objective of this study was to determine the ecotoxicity of AFFF, according to the type of fire to be fought (A1: 1.05g.L- 1, A2: 3.15g.L- 1 and A3: 6.30g.L- 1), to bioindicators of different trophic levels. For Artemia salina a toxic effect was observed at sample A1 (at concentrations of 100%), A2 (at concentrations above 25%) and A3 (at concentrations above 12.5%). For Lactuca sativa all samples affected the number of germinated seeds, speed and percentage of germination and root length. To the Eisenia fetida earthworm, samples A2 and A3 were considered toxic due to the percent avoidance being 70% and 100%, respectively. In Macaca mullata renal cell culture test, none of the samples were toxic by the MTT test. Therefore, it is necessary to develop methods for the safe use of AFFF by professionals.

Bioconcentration of Per- and Polyfluoroalkyl Substances and Precursors in Fathead Minnow Tissues Environmentally Exposed to Aqueous Film-Forming Foam-Contaminated Waters.

Exposure to per- and polyfluoroalkyl substances (PFAS) has been associated with toxicity in wildlife and negative health effects in humans. Decades of fire training activity at Joint Base Cape Cod (MA, USA) incorporated the use of aqueous film-forming foam (AFFF), which resulted in long-term PFAS contamination of sediments, groundwater, and hydrologically connected surface waters. To explore the bioconcentration potential of PFAS in complex environmental mixtures, a mobile laboratory was established to evaluate the bioconcentration of PFAS from AFFF-impacted groundwater by flow-through design. Fathead minnows (n = 24) were exposed to PFAS in groundwater over a 21-day period and tissue-specific PFAS burdens in liver, kidney, and gonad were derived at three different time points. The ∑PFAS concentrations in groundwater increased from approximately 10,000 ng/L at day 1 to 36,000 ng/L at day 21. The relative abundance of PFAS in liver, kidney, and gonad shifted temporally from majority perfluoroalkyl sulfonamides (FASAs) to perfluoroalkyl sulfonates (PFSAs). By day 21, mean ∑PFAS concentrations in tissues displayed a predominance in the order of liver > kidney > gonad. Generally, bioconcentration factors (BCFs) for FASAs, perfluoroalkyl carboxylates (PFCAs), and fluorotelomer sulfonates (FTS) increased with degree of fluorinated carbon chain length, but this was not evident for PFSAs. Perfluorooctane sulfonamide (FOSA) displayed the highest mean BCF (8700 L/kg) in day 21 kidney. Suspect screening results revealed the presence of several perfluoroalkyl sulfinate and FASA compounds present in groundwater and in liver for which pseudo-bioconcentration factors are also reported. The bioconcentration observed for precursor compounds and PFSA derivatives detected suggests alternative pathways for terminal PFAS exposure in aquatic wildlife and humans. Environ Toxicol Chem 2024;43:1795-1806. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Quantification of the variability and penetration of per- and poly-fluoroalkyl substances through a concrete pad

Historical use of aqueous film forming foams (AFFF) containing per- and poly-fluoroalkyl substances (PFAS) for fire-fighting activities has contributed to widespread contamination of infrastructure which can represent an ongoing source of PFAS to the surrounding environment. A concrete fire training pad with historical use of Ansulite and Lightwater AFFF formulations had PFAS concentrations measured to quantify spatial variability of PFAS within the pad. Surface chips and whole cores of concrete through to the underlying aggregate base were collected over the 24 × 9 m concrete pad and depth profiles of PFAS concentrations in nine cores were analysed. PFOS and PFHxS dominated the PFAS for surface samples, along the depth profile of cores and in the underlying plastic and aggregate material, with substantial variability in the concentrations of PFAS in the samples. Although there was variability of individual PFAS along the depth profile, higher surface concentrations of PFAS generally followed the designed movement of water across the pad. Total oxidisable precursor (TOP) assessments of one core indicated additional PFAS were present along the entire length of the core. This study highlights concentrations of PFAS (up to low μg/kg) from historical use of AFFF can occur throughout concrete, with the variable concentrations throughout the profile.

Comparison of PFAS soil remediation alternatives at a civilian airport using cost-benefit analysis

Contamination of soil and water systems by per- and polyfluoroalkyl substances (PFAS) due to uncontrolled use of aqueous film-forming foams (AFFFs) at firefighting training sites at civilian and military airports is a universal issue and can lead to significant human health and environmental impacts. Remediation of these sites is often complex but necessary to alleviate the PFAS burden and minimise the risks of exposure by eliminating the hotspot/source from which the PFAS spreads. This study presents a probabilistic cost-benefit analysis (CBA) for evaluating PFAS remediation alternatives, which includes monetisation of both direct costs and benefits as well as externalities. The method is applied for a case study to compare five remediation alternatives for managing PFAS contaminated soil at Stockholm Arlanda Airport in Sweden. The social profitability, or the net present value (NPV), of each remediation alternative was calculated in comparison to two reference alternatives – ‘total excavation’ of the site (Alt 0) or ‘do nothing’. Sensitivity analyses and model scenarios were tested to account for uncertainties, including small or large PFAS spreading and simulating different values for the magnitude of annual avoided cost of inaction (i.e., aggregate benefit) from PFAS remediation. In comparison to total excavation, four of the five studied remediation alternatives resulted in a positive mean NPV. Excavation and stabilization/solidification of the hotspot on-site combined with stabilization using activated carbon for the rest of site (Alt 2) had the highest NPV for both spreading scenarios, i.e., Alt 2 was the most socially profitable alternative. Simulations of the annual avoided cost of inaction enabled estimation of the breakeven point at which a remediation alternative becomes socially profitable (NPV > 0) compared to ‘do nothing’. Alt 2 had the lowest breakeven point: 7.5 and 5.75 millions of SEK/year for large and small spreading, respectively.

Visualization of the Distribution of PFOS and PFHxS in Concrete by DESI MSI

Firefighting training grounds (FTGs) may serve as a potential secondary source for the release of per- and polyfluoroalkyl substances (PFAS) due to historic use of aqueous film-forming foams (AFFFs). Understanding the heterogenicity and vertical distribution of PFAS in AFFF-impacted concrete is important for risk management and potential remediation. This study assessed whether desorption electrospray ionization mass spectrometry imaging (DESI MSI) can be used to analyze PFAS in a concrete core from an AFFF-impacted FTG to provide the vertical distribution of PFAS. PFOS and PFHxS were detected and observed to be distributed in the core mapped by DESI MSI in a manner consistent with data obtained using a conventional method of drilling samples along the depth of a concrete core (i.e., core sidewall drilling) followed by extraction into methanol and analysis by liquid chromatography mass spectrometry. Visualization by DESI MSI provided the mass distribution in greater detail at a resolution of 30–200 μm pixel size. DESI can provide location mapping at PFAS concentrations of >2.7 pg/mm2 (PFHxS) and 3.6 pg/mm2 (PFOS) with a spatial resolution much greater than that of the previously used core sidewall drilling method.

Liver and cardiometabolic markers and conditions in a cross-sectional study of three Australian communities living with environmental per- and polyfluoroalkyl substances contamination

Background: Per- and polyfluoroalkyl substances (PFAS) have been associated with higher cholesterol and liver function markers in some studies, but the evidence for specific cardiometabolic conditions has been inconclusive.Objectives: We quantified the associations of single and combined PFAS with cardiometabolic markers and conditions in a cross-sectional study of three Australian communities with PFAS-contaminated water from the historical use of aqueous film-forming foam in firefighting activities, and three comparison communities.Methods: Participants gave blood samples for measurement of nine PFAS, four lipids, six liver function markers, and completed a survey on sociodemographic characteristics and eight cardiometabolic conditions. We estimated differences in mean biomarker concentrations per doubling in single PFAS concentrations (linear regression) and per interquartile range increase in the PFAS mixture (Bayesian kernel machine regression). We estimated prevalence ratios of biomarker concentrations outside reference limits and self-reported cardiometabolic conditions (Poisson regression).Results: We recruited 881 adults in exposed communities and 801 in comparison communities. We observed higher mean total cholesterol with higher single and mixture PFAS concentrations in blood serum (e.g., 0.18 mmol/L, 95% credible interval −0.06 to 0.42, higher total cholesterol concentrations with an interquartile range increase in all PFAS concentrations in Williamtown, New South Wales), with varying certainty across communities and PFAS. There was less consistency in direction of associations for liver function markers. Serum perfluorooctanoic acid (PFOA) concentrations were positively associated with the prevalence of self-reported hypercholesterolemia in one of three communities, but PFAS concentrations were not associated with self-reported type II diabetes, liver disease, or cardiovascular disease.Discussion: Our study is one of few that has simultaneously quantified the associations of blood PFAS concentrations with multiple biomarkers and cardiometabolic conditions in multiple communities. Our findings for total cholesterol were consistent with previous studies; however, substantial uncertainty in our estimates and the cross-sectional design limit causal inference.

Psychological distress in three Australian communities living with environmental per- and polyfluoroalkyl substances contamination

BackgroundEnvironmental chemical contamination is a recognised risk factor for psychological distress, but has been seldom studied in the context of per- and polyfluoroalkyl substances (PFAS) contamination. We examined psychological distress in a cross-sectional study of three Australian communities exposed to PFAS from the historical use of aqueous film-forming foam in firefighting activities, and three comparison communities without environmental contamination. MethodsParticipation was voluntary following recruitment from a PFAS blood-testing program (exposed) or random selection (comparison). Participants provided blood samples and completed a survey on their exposure history, sociodemographic characteristics, and four measures of psychological distress (Kessler-6, Distress Questionnaire-5, Patient Health Questionnaire-15, and Generalised Anxiety Disorder-7). We estimated prevalence ratios (PR) of clinically-significant psychological distress scores, and differences in mean scores: (1) between exposed and comparison communities; (2) per doubling in PFAS serum concentrations in exposed communities; (3) for factors that affect the perceived risk of living in a community exposed to PFAS; and (4) in relation to self-reported health concerns. ResultsWe recruited 881 adults in exposed communities and 801 in comparison communities. We observed higher levels of self-reported psychological distress in exposed communities than in comparison communities (e.g., Katherine compared to Alice Springs, Northern Territory: clinically-significant anxiety scores, adjusted PR = 2.82, 95 % CI 1.16–6.89). We found little evidence to suggest that psychological distress was associated with PFAS serum concentrations (e.g., Katherine, PFOS and anxiety, adjusted PR = 0.85, 95 % CI 0.65–1.10). Psychological distress was higher among exposed participants who were occupationally exposed to firefighting foam, used bore water on their properties, or were concerned about their health. ConclusionPsychological distress was substantially more prevalent in exposed communities than in comparison communities. Our findings suggest that the perception of risks to health, rather than PFAS exposure, contribute to psychological distress in communities with PFAS contamination.

Perfluoroalkyl substances exposure in firefighters: Sources and implications

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

Exposure Trends and Half-lives of Per- and Polyfluoroalkyl Substances (PFAS) in Australian Firefighters

BACKGROUND AND AIM: Per- and polyfluoroalkyl substances (PFASs) are persistent manmade compounds used in aqueous film forming foam (AFFF). The extensive use of AFFF has led to widespread environmental PFAS contamination and exposures to firefighters. The aim of this study is to determine PFAS blood serum concentration trends and apparent serum elimination half-lives in firefighters after the replacement of AFFF. METHODS: Current and former employees of an Australian corporation providing aviation firefighting services, where AFFF had been used in the past, were recruited to participate in this study. Special focus was placed on re-recruiting participants who had provided blood samples five years prior. Participants were asked to provide a blood sample and complete a questionnaire. Serum samples were analysed for 40 different PFASs using HP LC-MS/MS. RESULTS: A total of 799 participants provided blood samples. Of these, 130 previously provided blood serum five years prior. Mean serum concentrations of perfluorooctane sulfonate (PFOS, 27 ng/mL), perfluoroheptane sulfonate (PFHpS, 1.7 ng/mL) and perfluorohexane sulfonate (PFHxS, 14 ng/mL) were significantly higher than the levels in the general Australian population. Serum concentrations were associated with the use of PFOS/PFHxS based AFFF. Participants who commenced service after the replacement of this foam had serum concentrations similar to those in the general Australian population. Average individual apparent half-lives were estimated to be 5.0 years (perfluorooctanoic acid (PFOA)), 7.8 years (PFHxS), 7.4 years (PFHpS) and 6.5 years (PFOS). CONCLUSIONS: This study shows how workplace interventions such as replacement of AFFF, can benefit employees at risk of occupational exposure. KEYWORDS: Biological Monitoring Occupational Exposure Firefighters Follow-Up Studies Half-Life

Serum concentration trends and apparent half-lives of per- and polyfluoroalkyl substances (PFAS) in Australian firefighters.

Per- and polyfluoroalkyl substances (PFASs) are persistent manmade compounds used in aqueous film forming foam (AFFF). The extensive use of AFFF has led to widespread environmental PFAS contamination and exposures of firefighters. To determine PFAS blood serum concentration trends and apparent serum half-lives in firefighters after the replacement of AFFF. Current and former employees of an Australian corporation providing firefighting services, where AFFF formulations had been used since the 1980s up until 2010, were recruited in 2018-2019 to participate in this study. Special focus was put on re-recruiting participants who had provided blood samples five years prior (2013-2014). Participants were asked to provide a blood sample and fill in a questionnaire. Serum samples were analysed for 40 different PFASs using HP LC-MS/MS. A total of 799 participants provided blood samples in 2018-2019. Of these, 130 previously provided blood serum in 2013-2014. In 2018-2019, mean (arithmetic) serum concentrations of perfluorooctane sulfonate (PFOS, 27ng/mL), perfluoroheptane sulfonate (PFHpS, 1.7ng/mL) and perfluorohexane sulfonate (PFHxS, 14ng/mL) were higher than the levels in the general Australian population. Serum concentrations were associated with the use of PFOS/PFHxS based AFFF. Participants who commenced service after the replacement of this foam had serum concentrations similar to those in the general population. Mean (arithmetic) individual apparent half-lives were estimated to be 5.0 years (perfluorooctanoic acid (PFOA)), 7.8 years (PFHxS), 7.4 years (PFHpS) and 6.5 years (PFOS). This study shows how workplace interventions such as replacement of AFFF can benefit employees at risk of occupational exposure.

Pilot study comparison of regenerable and emerging single-use anion exchange resins for treatment of groundwater contaminated by per- and polyfluoroalkyl substances (PFASs)

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 (logKex) 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.

Study on Environmental Regulation of Aqueous Film Forming Foam and Use of C4-Based Eco-Friendly Aqueous Film Forming Foam

The C8-based aqueous film forming foam (AFFF) was developed by 3M in 1960, initially for military purposes, and was then used in all U.S. Navy vessels until the late 1960s. The U.S. Department of Defense used the AFFF for fuel fire suppression in all military facilities in the 1970s. The AFFF was classified as a special fire extinguishing chemical used for an airplane hangar or an aircraft carrier. Despite its strong fire extinguishing capacity, the AFFF is not commonly used by civilians, mainly due to the cost factor and environmental issues. In particular, the main organic chemical component of the AFFF is resistant to degradation; it tends to persist in the ecological system and in the human body, consequently having grievous effects. The paper describes the causes and measures of the AFFF use regulations by the Stockholm Convention concerning persistent organic chemicals. The manuscript also introduces the C4-based eco-friendly AFFF, a fire extinguishing chemical developed in China, as a part of the measure and addresses the meaning of “C4-Based.” Moreover, the study verifies that the representative regulation targets for perfluorooctane sulfonates (PFOS) and perfluorooctanoic acid (PFOA) are not detected in the C4-based eco-friendly AFFF fire extinguishing chemical, as revealed by a test on “the method for analyzing PFOS/PFOA” in the chemical product based on the National Standard Test KS M 9722:2017. Accordingly, various fire extinguishers using the C4-based eco-friendly AFFF with strong and extensive fire extinguishing capacity are proposed, and the other use methods.

Assessment of per- and polyfluoroalkyl substances (PFAS) in the Indian River Lagoon and Atlantic coast of Brevard County, FL, reveals distinct spatial clusters

Per- and polyfluoroalkyl substances (PFAS) constitute a class of highly stable and extensively manufactured anthropogenic chemicals that have been linked to a variety of adverse health effects in humans and wildlife. These compounds are ubiquitously distributed in the environment and have been measured in aquatic systems globally. However, there are limited data on longitudinal comprehensive assessments of PFAS profiles within sensitive aquatic ecosystems. Surface water samples were collected from the Indian River Lagoon (IRL) and the Atlantic coast within Brevard County (BC), FL in December of 2019 (n = 57) and again from corresponding locations in February of 2021 (n = 40). Samples were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to determine the occurrence, concentration, and distribution of 92 PFAS. No significant difference in total PFAS concentrations were identified between samples collected in 2019 (87 ng/L) and those collected in 2021 (77 ng/L). However, comparisons of PFAS among four natural sub-regions within Brevard County revealed site- and regional-specific differences. The Banana River exhibited the greatest concentration of total PFAS, followed by the southern Indian River, the northern Indian River, and then the Atlantic coast. Six distinct PFAS profiles were identified with the novel application of multivariate statistical cluster analysis, which may be useful for identifying potential sources of PFAS. Elevated total PFAS and unique compound mixtures identified in the Banana River are most likely a result of industrial discharge and extensive historical use of aqueous film-forming foams (AFFF). The environmental persistence of PFAS threatens key ecosystem services and the ecological homeostasis of the Indian River Lagoon – the most biologically diverse estuary in North America. Brevard County offers a unique model site that may be used to investigate potential exposure and health implications for wildlife and adjacent coastal communities, which could be extrapolated to better understand and manage other critical coastal systems.

Method for extraction and analysis of per- and poly-fluoroalkyl substances in contaminated asphalt.

The legacy use of aqueous film-forming foam (AFFF) has led to the generation of large volumes of per- and poly-fluoroalkyl substances (PFAS)-contaminated asphalt materials, especially at airports and fire training areas. The management of such PFAS-contaminated asphalt materials requires an understanding of PFAS concentrations in these materials. This study, therefore, aimed to develop a suitable extraction methodology for the analysis of 22 target PFAS (i.e., carboxylic acids, sulfonic acids and fluorotelomers) in asphalt materials. A series of experiments was conducted to optimise extraction solvent composition, as well as to assess the performance of the chosen method under various conditions (i.e., sonication temperature, PFAS contamination level, asphalt core composition and timing of stable isotope addition used as internal standard). The methanol-based extractants performed best due to their accuracy and precision, which were within the acceptable range (extraction efficiency between 70 and 130% and RSD < 20%). The method which involved three successive extractions with methanol/1% NH3 by ultrasonication at 25 °C was selected due to its performance and ease of operation. The mean recovery of a vast majority of PFAS was found to be in the acceptable range. Tests on the timing of addition of stable isotope (SI)-labelled PFAS internal standards indicate that the recoveries obtained, regardless of when the stable isotopes were added, were within the acceptable range for PFAS. The accuracy and precision of PFAS recoveries were not affected by PFAS spike level (2 μg kg-1 and 200 μg kg-1), as well as sample composition (based on the location of asphalt material in the field). Low RSDs were achieved for asphalt cores collected from a contaminated site covering a wide range of concentrations (from LOQ to 2135 mg kg-1), demonstrating the suitability of the sample preparation method for real-world samples. The results from the interlaboratory testing were also in good agreement and validated the proposed PFAS extraction and analytical approach.

Simulating Impacts of Biosparging on Release and Transformation of Poly- and Perfluorinated Alkyl Substances from Aqueous Film-Forming Foam-Impacted Soil

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 O2-sparged columns compared to N2-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.

Geographic and Demographic Variability in Serum PFAS Concentrations for Pregnant U.S. Women

BACKGROUND AND AIM: The National Children’s Study (NCS) Vanguard Study pilot tested recruitment methods and protocols designed for the NCS Main Study. Over 1,000 pregnant women from seven counties throughout the U.S. were recruited during 2009 and 2010 to assess relationships between environmental and other exposures and children’s health in a nationally representative longitudinal birth cohort study. Women had at least one home visit during pregnancy to collect biomonitoring specimens, environmental samples, and questionnaire data. METHODS: Here we analyzed data from the NCS Vanguard Study Vanguard Data and Sample Archive Access System for PFAS concentrations in the serum of 427 pregnant women. Geographic variability in serum concentrations was investigated through summary statistics and tests of difference between sampling locations. The cohort was organized into self-reported demographic groups based on income, home age, and drinking water source. Variability in serum concentrations between these groups was used to target spatial mapping analyses that incorporated public data from the U.S. census, drinking water measurements, and PFAS-related industry locations. RESULTS:Statistically significant differences in serum concentration means were observed among the seven counties. Higher PFOA serum concentrations were observed in lower income participants in Montgomery County, PA whereas the opposite was observed in other counties. Spatial analyses demonstrated that these lower income participants were likely exposed to contaminated drinking water from aqueous film-forming foam use at a nearby military base, explaining higher serum levels. CONCLUSIONS:Our analysis of NCS Vanguard Study data improves understanding of relative importance of PFAS exposure sources and associations at the community and household levels. By better identifying vulnerable populations and locations with high potential PFAS exposures, this work contributes to risk management strategies that maximize public health protection. Disclaimer: The views expressed in this presentation are those of the authors and do not necessarily represent the views or policies of the U.S. Environmental Protection Agency. KEYWORDS: PFAS, pregnant women, spatial analysis

Hydrothermal Alkaline Treatment for Destruction of Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foam

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. 19F 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 (PFAS) and total fluorine in fire station dust.

Per- and polyfluoroalkyl substances (PFAS) are a class of over 4,700 fluorinated compounds used in industry and consumer products. Studies have highlighted use of aqueous film-forming foams (AFFFs) as an exposure source for firefighters, but little is known about PFAS occurrence inside fire stations, where firefighters spend most of their shifts. In this study, we aimed to characterize PFAS concentrations and sources inside fire stations. We measured 24 PFAS (using LC-MS/MS) and total fluorine (using particle-induced gamma ray emission) in dust from multiple rooms of 15 Massachusetts stations, many of which (60%) no longer use PFAS-containing AFFF at all and the rest of which only use it very rarely. Compared to station living rooms, turnout gear locker rooms had higher dust levels of total fluorine (p<0.0001) and three PFAS: perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), and perfluorodecanoate (PFDoDA) (p<0.05). These PFAS were also found on six wipes of station turnout gear. By contrast, the dominant PFAS in living rooms was N-ethyl perfluorooctane sulfonamidoacetic acid (N-MeFOSAA), a precursor to perfluorooctane sulfonate (PFOS) that still persists despite phase-outs almost two decades ago. The Σ24PFAS accounted for less than 2% of fluorine in dust (n=39), suggesting the potential presence of unknown PFAS. Turnout gear may be an important PFAS source in stations due to intentional additives and/or contamination from firefighting activities.

Sensitivity and Accumulation of Perfluorooctanesulfonate and Perfluorohexanesulfonic Acid in Fathead Minnows (Pimephales promelas) Exposed over Critical Life Stages of Reproduction and Development.

Per- and polyfluoroalkyl substances (PFAS) have emerged as contaminants of environmental concern following release from industrial practices and use of aqueous film-forming foam (AFFF). Of the identified PFAS in surface water samples from known AFFF release sites, perfluorooctanesulfonate (PFOS) and perfluorohexanesulfonic acid (PFHxS) are frequently detected. The focus of the present study was to determine the effects of PFOS and PFHxS to the native (and common) fathead minnow, Pimephales promelas, over critical life stages of reproduction and development. Two separate, 42-d experiments were carried out using sexually mature fish, exposed to either PFOS or PFHxS. Measured exposure concentrations for PFOS and PFHxS were 0, 44, 88, 140, and 231 µg/L and 0, 150, 300, 600, and 1200 µg/L, respectively. At day 21 of the adult exposure, eggs were collected and reared for 21 d to determine the effects of PFOS or PFHxS on development, growth, and survival of larvae. The no-observable-effect concentration (NOEC) for PFOS was 44 µg/L, and the lowest-observable-effect concentration was 88 µg/L based on reduced growth in juvenile (F1) fish. Effects from PFOS exposures that did not follow a standard dose-response curve were reduced gonadosomatic index in adult males (at 44 µg/L) and reduced fecundity in females (at 140 µg/L). There was no toxicity on apical endpoints to report on adult or juvenile fish exposed to PFHxS up to 1200 µg/L. Importantly, we note that both PFOS and PFHxS accumulated in gonads and liver of adult fish following the respective exposures. The present study supports previous literature on PFOS toxicity and accumulation in fathead minnows but resulted in a lower NOEC than previously established for this species. Environ Toxicol Chem 2021;40:811-819. © 2020 SETAC.