This data release presents chemical and biological results from an investigation of the uptake of per- and polyfluoroalkyl substances (PFAS) from groundwater contaminated by fire training activities on Cape Cod, Massachusetts. Exposure experiments were conducted from August 29 to September 21, 2018 using groundwater from a relatively uncontaminated reference site and a fire training area contaminated site. To assess the uptake characteristics of the PFAS mixtures present in the 2 groundwater sources, 21-day mobile laboratory exposure experiments were conducted using fathead minnows (Pimephales promelas), polar organic chemical integrative samplers, and polyethylene tube samplers. Freshwater mussel (Ligumia subrostrata) exposure experiments were conducted for 14 days, beginning on day 7 of the fish and passive sampler exposures. Groundwater samples were collected daily (with a few exceptions). Samples for male fish and passive samplers were collected on days 0, 4, 7, 14, and 21. Samples for female fish were collected on days 0, 7, 14, and 21. The 14 day mussel exposures began on day 7 of the fish and passive sampler exposures, and mussel samples were collected on days 7, 11, 14, and 21. Groundwater site locations and well characteristics are presented in Table 1. Information on the various PFAS and co-occurring contaminants measured in the different media are presented in Table 2. Quality assurance results for PFAS analysis of the different media are presented in Table 3. Results for PFAS in groundwater are presented in Table 4. Results for co-occurring contaminants in groundwater are presented in Table 5. Results for fish biomarkers are presented in Table 6. Results for PFAS in male and female fish tissue are presented in Table 7. Results for PFAS in mussel tissue are presented in Table 8. Results for PFAS in polar organic chemical integrative samplers are presented in Table 9. Results for PFAS in polyethylene tube samplers are presented in Table 10.
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 > 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. 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.
Uptake of Per- and Polyfluoroalkyl Substances by Fish, Mussel, and Passive Samplers in Mobile-Laboratory Exposures Using Groundwater from a Contamination Plume at a Historical Fire Training Area, Cape Cod, Massachusetts
Abstract. Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive
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
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.
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)"
Centurial Persistence of Forever Chemicals at Military Fire Training Sites
Abstract. Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases t
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
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
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
Diffusive-Gradient Passive Samplers for Per- and Polyfluoroalkyl Substances.
Per- and polyfluoroalkyl substances (PFAS) are chemical pollutants of growing concern. Due to their ubiquity, persistence in the environment, and potential for toxicity at low environmental concentrations, it is necessary to have convenient and reliable methods to measure PFAS in natural waters. Passive sampling methods (in situ pre-concentration of PFAS) are investigated for monitoring purposes. The following dataset specifically deals with the calibration and application of a diffusive gradient in thin film (DGT) passive sampler, as well as comparisons to previously designed microporous polyethylene tube (MPT) passive samplers and water grab samples. Concentrations are measured with tandem liquid-chromatography mass spectrometry (LC-MS/MS) for all sampling methods. The dataset comprises: (i) a list of 25 PFAS compounds considered for the study at hand, (ii) method detection limits of considered PFAS compounds, (iii) calibration experiments of the DGT passive sampler, as well as results from modelling approaches to determine sampling rates, (iv) lab deployment of the developed DGT to challenge determined sampling rates, (v) field deployments of the developed DGT in an assortment of streams, ponds, and lakes in Minnesota and Maine, where concentrations of PFAS compounds are compared to concentrations measured by MPT, and water grab samples.
Tap Water Contributions to Plasma Concentrations of Poly- and Perfluoroalkyl Substances (PFAS) in a Nationwide Prospective Cohort of U.S. Women
Abstract Background: Between 2013 and 2015, concentrations of poly- and perfluoroalkyl substances (PFAS) in public drinking water supplies serving at least six million individuals exceeded the level set forth in the health advisory established by the U.S. Environmental Protection Agency. Other than data reported for contaminated sites, no systematic or prospective data exist on the relative source contribution (RSC) of drinking water to human PFAS exposures. Objectives: This study estimates the RSC of tap water to overall PFAS exposure among members of the general U.S. population. Methods: We measured concentrations of 15 PFAS in home tap water samples collected in 1989–1990 from 225 participants in a nationwide prospective cohort of U.S. women: the Nurses’ Health Study (NHS). We used a one-compartment toxicokinetic model to estimate plasma concentrations corresponding to tap water intake of PFAS. We compared modeled results with measured plasma PFAS concentrations among a subset of 110 NHS participants. Results: Tap water perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) were statistically significant predictors of plasma concentrations among individuals who consumed ≥8 cups of tap water per day. Modeled median contributions of tap water to measured plasma concentrations were: PFOA 12% (95% probability interval 11%–14%), PFNA 13% (8.7%–21%), linear perfluorooctanesulfonic acid (nPFOS) 2.2% (2.0%–2.5%), branched perfluorooctanesulfonic acid (brPFOS) 3.0% (2.5%–3.2%), and perfluorohexanesulfonic acid (PFHxS) 34% (29%–39%). In five locations, comparisons of PFASs in community tap water collected in the period 2013–2016 with samples from 1989–1990 indicated increases in quantifiable PFAS and extractable organic fluorine (a proxy for unquantified PFAS). Conclusions: Our results for 1989–1990 compare well with the default RSC of 20% used in risk assessments for legacy PFAS by many agencies. Future evaluation of drinking water exposures should incorporate emerging PFAS. https://doi.org/10.1289/EHP4093
Uptake of hydrophobic organic compounds, including organochlorine pesticides, polybrominated diphenyl ethers, and perfluoroalkyl acids in fish and blue crabs of the lower Passaic River, New Jersey, USA
Abstract . The bioavailability and bioaccumulation of sedimentary hydrophobic organic compounds (HOCs) is of concern at contaminated sites. Passive sampler
Delayed discovery, dissemination, and decisions on intervention in environmental health: a case study on immunotoxicity of perfluorinated alkylate substances
Identification and characterization of environmental hazards that impact human health must rely on the best possible science to inform and inspire appropriate public health intervention. The perfluorinated alkylate substances (PFASs) are persistent emerging pollutants that are now being recognized as important human health hazards. Although the PFASs have been produced for over 60 years, academic research on environmental health aspects has appeared only in the most recent 10 years or so. In the meantime, these persistent chemicals accumulated in the global environment. Some early studies e.g., on population exposures and toxicity, were not released to the public until after year 2000. Still, the first PFAS risk assessments ignored these reports and relied on scant journal publications. The first guidelines and legal limits for PFAS exposure, e.g., from drinking water, were proposed 10 years ago. They have decreased substantially since then, but remain higher than suggested by data on human adverse effects, especially on the immune system, that occur at background exposure levels. By now, the best-known PFASs are being phased out, and related PFASs are being introduced as substitutes. Given the substantial delays in discovery of PFAS toxicity, in dissemination of findings, and in regulatory decisions, PFAS substitutes and other persistent industrial chemicals should be subjected to prior scrutiny before widespread usage.
Isolating the AFFF Signature in Coastal Watersheds Using Oxidizable PFAS Precursors and Unexplained Organofluorine
Abstract. Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary an
Field Validation of a Novel Passive Sampler for Dissolved PFAS in Surface Waters
Abstract Numerous per- and polyfluoroalkyl substances (PFAS) are of growing concern worldwide due to their ubiquitous presence, bioaccumulation and adverse effects. Surface waters in the United States have displayed elevated concentrations of PFAS, but so far discrete water sampling has been the commonly applied sampling approach. In the present study we field-tested a novel integrative passive sampler, a microporous polyethylene tube, and derived sampling rates (Rs) for nine PFAS in surface waters. Three sampling campaigns were conducted, deploying polyethylene tube passive samplers in the effluent of two wastewater treatment plant (WWTP) effluents and across Narragansett Bay (Rhode Island, USA) for 1 month each in 2017 and 2018. Passive samplers exhibited linear uptake of PFAS in the WWTP effluents over 16–29 days, with in situ Rs for nine PFAS ranging from 10 ml day−1 (perfluoropentanoic acid) to 29 ml day−1 (perfluorooctanesulfonic acid). Similar sampling rates of 19 ± 4.8 ml day−1 were observed in estuarine field deployments. Applying these Rs values in a different WWTP effluent predicted dissolved PFAS concentrations mostly within 50% of their observations in daily composite water samples, except for perfluorobutanoic acid (where predictions from passive samplers were 3 times greater than measured values), perfluorononanoic acid (1.9 times), perfluorodecanoic acid (1.7 times), and perfluoropentanesulfonic acid (0.1 times). These results highlight the potential use of passive samplers as measurement and assessment tools of PFAS in dynamic aquatic environments. Environ Toxicol Chem 2022;41:2375–2385. © 2022 SETAC Abstract A novel integrative passive sampler was field-tested and sampling rates derived for nine per- and polyfluoroalkyl substances in two wastewater treatment plant effluents and in Narragansett Bay surface waters.
Can profiles of poly- and Perfluoroalkyl substances (PFASs) in human serum provide information on major exposure sources?
Humans are exposed to poly- and perfluoroalkyl substances (PFASs) from diverse sources and this has been associated with negative health impacts. Advances in analytical methods have enabled routine detection of more than 15 PFASs in human sera, allowing better profiling of PFAS exposures. The composition of PFASs in human sera reflects the complexity of exposure sources but source identification can be confounded by differences in toxicokinetics affecting uptake, distribution, and elimination. Common PFASs, such as perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) and their precursors are ubiquitous in multiple exposure sources. However, their composition varies among sources, which may impact associated adverse health effects.
