Isolating the AFFF Signature in Coastal Watersheds Using Oxidizable PFAS Precursors and Unexplained Organofluorine

High organofluorine concentrations in municipal wastewater affect downstream drinking water supplies for millions of Americans

Wastewater receives per- and polyfluoroalkyl substances (PFAS) from diverse consumer and industrial sources, and discharges are known to be a concern for drinking water quality. The PFAS family includes thousands of potential chemical structures containing organofluorine moieties. Exposures to a few well-studied PFAS, mainly perfluoroalkyl acids (PFAA), have been associated with increased risk of many adverse health outcomes, prompting federal drinking water regulations for six compounds in 2024. Here, we find that the six regulated PFAS (mean = 7 to 8%) and 18 measured PFAA (mean = 11 to 21%) make up only a small fraction of the extractable organofluorine (EOF) in influent and effluent from eight large municipal wastewater treatment facilities. Most of the EOF in influent (75%) and effluent (62%) consists of mono- and polyfluorinated pharmaceuticals. The treatment technology and sizes of the treatment facilities in this study are similar to those serving 70% of the US population. Despite advanced treatment technologies, the maximum EOF removal efficiency among facilities in this work was <25%. Extrapolating our measurements to other large facilities across the United States results in a nationwide EOF discharge estimate of 1.0 to 2.8 million moles F y −1 . Using a national model that simulates connections between wastewater discharges and downstream drinking water intakes, we estimate that the sources of drinking water for up to 23 million Americans could be contaminated above regulatory thresholds by wastewater-derived PFAS alone. These results emphasize the importance of further curbing ongoing PFAS sources and additional evaluations of the fate and toxicity of fluorinated pharmaceuticals.

Sociodemographic Factors Are Associated with the Abundance of PFAS Sources and Detection in U.S. Community Water Systems

Abstract. Drinking water contaminated by per- and polyfluoroalkyl substances (PFAS) is a widespread public health concern, and exposure–response relationsh

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

Dataset of targeted PFAS and extractable organofluorine concentrations in water, sediment, and biological tissue samples that support data included in two papers: "Characterizing the Areal Extent of PFAS Contamination in Fish Species Downgradient of AFFF Source Zones" and "Bioaccumulation of Perfluoroalkyl Sulfonamides (FASA)"

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

Abstract. Most monitoring programs next to large per- and polyfluoroalkyl substances (PFAS) sources focus on drinking water contamination near source zones

Addressing Urgent Questions for PFAS in the 21st Century

Abstract. Despite decades of research on per- and polyfluoroalkyl substances (PFAS), fundamental obstacles remain to addressing worldwide contamination by

Characterization of the Potential Long-Term Impact from Sedimentary PFAS at a Historically Contaminated Textile Waste Site

Abstract. Per- and polyfluoroalkyl substances (PFAS) are pervasive pollutants at historically contaminated sites throughout the United States and beyond. T

Characterization of the Potential Long-Term Impact from Sedimentary PFAS at a Historically Contaminated Textile Waste Site

Abstract. Per- and polyfluoroalkyl substances (PFAS) are pervasive pollutants at historically contaminated sites throughout the United States and beyond. T

A review of the pathways of human exposure to poly- and perfluoroalkyl substances (PFASs) and present understanding of health effects

Here, we review present understanding of sources and trends in human exposure to poly- and perfluoroalkyl substances (PFASs) and epidemiologic evidence for impacts on cancer, immune function, metabolic outcomes, and neurodevelopment. More than 4000 PFASs have been manufactured by humans and hundreds have been detected in environmental samples. Direct exposures due to use in products can be quickly phased out by shifts in chemical production but exposures driven by PFAS accumulation in the ocean and marine food chains and contamination of groundwater persist over long timescales. Serum concentrations of legacy PFASs in humans are declining globally but total exposures to newer PFASs and precursor compounds have not been well characterized. Human exposures to legacy PFASs from seafood and drinking water are stable or increasing in many regions, suggesting observed declines reflect phase-outs in legacy PFAS use in consumer products. Many regions globally are continuing to discover PFAS contaminated sites from aqueous film forming foam (AFFF) use, particularly next to airports and military bases. Exposures from food packaging and indoor environments are uncertain due to a rapidly changing chemical landscape where legacy PFASs have been replaced by diverse precursors and custom molecules that are difficult to detect. Multiple studies find significant associations between PFAS exposure and adverse immune outcomes in children. Dyslipidemia is the strongest metabolic outcome associated with PFAS exposure. Evidence for cancer is limited to manufacturing locations with extremely high exposures and insufficient data are available to characterize impacts of PFAS exposures on neurodevelopment. Preliminary evidence suggests significant health effects associated with exposures to emerging PFASs. Lessons learned from legacy PFASs indicate that limited data should not be used as a justification to delay risk mitigation actions for replacement PFASs.

Guideline levels for PFOA and PFOS in drinking water: the role of scientific uncertainty, risk assessment decisions, and social factors

Communities across the U.S. are discovering drinking water contaminated by perfluoroalkyl and polyfluoroalkyl substances (PFAS) and determining appropriate actions. There are currently no federal PFAS drinking water standards despite widespread drinking water contamination, ubiquitous population-level exposure, and toxicological and epidemiological evidence of adverse health effects. Absent federal PFAS standards, multiple U.S. states have developed their own health-based water guideline levels to guide decisions about contaminated site cleanup and drinking water surveillance and treatment. We examined perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) water guideline levels developed by the U.S. Environmental Protection Agency (EPA) and state agencies to protect people drinking the water, and summarized how and why these levels differ. We referenced documents and tables released in June 2018 by the Interstate Technology and Regulatory Council (ITRC) to identify states that have drinking water and groundwater guideline levels for PFOA and/or PFOS that differ from EPA’s health advisories (HAs). We also gathered assessment documents from state websites and contacted state environmental and health agencies to identify and confirm current guidelines. Seven states have developed their own water guideline levels for PFOA and/or PFOS ranging from 13 to 1000 ng/L, compared to EPA’s HA of 70 ng/L for both compounds individually or combined. We find that the development of PFAS guideline levels via exposure and hazard assessment decisions is influenced by multiple scientific, technical, and social factors, including managing scientific uncertainty, technical decisions and capacity, and social, political, and economic influences from involved stakeholders. Assessments by multiple states and academic scientists suggest that EPA’s HA is not sufficiently protective. The ability of states to develop their own guideline levels and standards provides diverse risk assessment approaches as models for other state and federal regulators, while a sufficiently protective, scientifically sound, and enforceable federal standard would provide more consistent protection.

PFAS and Precursor Bioaccumulation in Freshwater Recreational Fish: Implications for Fish Advisories

Abstract. Per- and polyfluoroalkyl substances (PFAS) are a diverse class of fluorinated anthropogenic chemicals that include perfluoroalkyl acids (PFAA), w

TrifluoroaceticAcid (TFA) Exceeds All Other ExtractableOrganofluorine in Drinking Water from Eastern Massachusetts, UnitedStates

Abstract Per- and polyfluoroalkyl substances (PFAS) are present in drinking water consumed by ∼200 million United States (US) residents, but many are not detected by routine monitoring methods. Here, we aimed to better characterize the organofluorine mass budget in US drinking water samples from 19 sites in eastern Massachusetts. Extractable organofluorine (EOF) was detected at 16/17 sites served by community water systems (CWS) using conventional treatment techniques (coagulation, flocculation, clarification, and filtration). At these sites, a suite of 37 targeted PFAS accounted for 6–68% of the EOF and suspect screening identified fluorinated agrochemicals in almost all samples. High EOF concentrations in untreated source waters for two CWS that used granular activated carbon (GAC) and ion-exchange (IX) treatment, were reduced below detection in finished drinking water samples. Our EOF measurements were not selective for trifluoroacetic acid (TFA), so we measured concentrations in triplicate samples at one conventional treatment site and from the IX and GAC sites. At these sites, TFA concentrations were higher than those of EOF and were unaffected by the treatment type. Results of this pilot study show GAC and IX treatment removed virtually all organofluorine in drinking water other than TFA.

Poly- and Perfluoroalkyl Substances in Seawater and Plankton from the Northwestern Atlantic Margin

Abstract. The ocean is thought to be the terminal sink for poly- and perfluoroalkyl substances (PFAS) that have been produced and released in large quantit

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

Abstract 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 &gt; kidney &gt; 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. Flow-through dosing experiments utilizing aqueous film-forming foam (AFFF)–contaminated groundwater revealed positive linear correlations between fluorinated carbon chain length and logarithm-transformed bioconcentration factors (BCFs) for perfluoroalkyl sulfonamides identified in fathead minnow (Pimephales promelas) liver via target analysis and suspect screening using high-resolution mass spectrometry. FBSA = perfluorobutane sulfonamide; FHxSA = perfluorohexane sulfonamide; FOSA = perfluorooctane sulfonamide; FPeSA= perfluoropentane sulfonamide; FPrSA = perfluoropropane sulfonamide.

Passive Sampler Derived Profiles and Mass Flows of Perfluorinated Alkyl Substances (PFASs) across the Fram Strait in the North Atlantic

Abstract. Per- and polyfluorinated alkyl substances (PFAS) are a family of pollutants of high concern due to their ubiquity and negative human health impac

Transport of Legacy Perfluoroalkyl Substances and the Replacement Compound HFPO-DA through the Atlantic Gateway to the Arctic Ocean—Is the Arctic a Sink or a Source?

Abstract. The spatial distribution of 29 per- and polyfluoroalkyl substances (PFASs) in seawater was investigated along a sampling transect from Europe to

Interlaboratory Comparison of Extractable Organofluorine Measurements in Groundwater and Eel ( <i>Anguilla rostrata</i> ): Recommendations for Methods Standardization

Abstract. Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could suppo