Field Validation of a Novel Passive Sampler for Dissolved PFAS in Surface Waters

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.

PFAS Sampling Rates in Microporous Polyethylene Tube Samplers

<p><strong>Dataset Description</strong></p> <p> This dataset contains PFAS water concentrations measured using grab samples and PFAS accumulated in microporous polyethylene tube (MPT) passive samplers across five field campaigns. These data were used to reevaluate PFAS sampling rates for MPT passive samplers. An overview of sampling sites and sources of temperature data used in the reevaluation is also provided. </p> <p> The five field campaigns are labeled according to principal investigator and field site: </p> <ul> <li><strong>CG_RI</strong>: Christine Gardiner, Narragansett Bay, Rhode Island</li> <li><strong>JS_DU</strong>: Jarod Snook, Duluth, Minnesota</li> <li><strong>JS_ME</strong>: Jarod Snook, Maine</li> <li><strong>MD_CC</strong>: Matthew Dunn, Cape Cod, Massachusetts</li> <li><strong>MD_WE</strong>: Matthew Dunn, Westerly, Rhode Island</li> </ul> <p> For each field campaign, a README file is included that provides the information necessary to locate, interpret, and reuse the associated data. For studies conducted by Jarod Snook, raw data files are provided directly. </p> <p> Cleaned and compiled datasets are provided as <em>grab_samples.csv</em>, containing data from grab samples, and <em>pe_tube.csv</em>, containing data from MPT deployments, grab samples, and re-evaluated sampling rates. </p> <p> Compound and water type specific PFAS sampling rates derived from averaged values and multiple fitting approaches (linear, inverse linear, and exponential) are provided alongside reference sampling rate data from Australia and Spain in <em>parameters_fresh_salt.csv</em> and <em>parameters_ground.csv</em>, respectively. </p>

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.

Calibration of Perfluorinated Alkyl Acid Uptake Rates by a Tube Passive Sampler in Water

Abstract. Per- and polyfluoroalkyl substances (PFAS) are a group of 4000+ man-made compounds of great concern due to their environmental ubiquity and adver

PFAS Statewide Sampling Dataset: PFAS drinking water sampling data from U.S. community water systems

This repository contains a sample of U.S. community water systems (CWS) included in the PFAS statewide sampling dataset. In the first versions of this dataset, 18 states were included as part of Liddie et al., 2023. The statewide sampling dataset now includes compiled data from 28 U.S. statewide sampling campaigns of CWS for per- and polyfluoroalkyl substances (PFAS) in drinking water. The full dataset of samples spans the 2016-2024 period. All data were either publicly available or provided by state agencies upon request. The full dataset contains approximately 98,000 samples from 11,138 CWS in Alabama, Arizona, California, Colorado, Georgia, Illinois, Indiana, Iowa, Kentucky, Maine, Maryland, Massachusetts, Michigan, Minnesota, Missouri, New Hampshire, New Jersey, New York, Ohio, Pennsylvania, Rhode Island, South Carolina, Tennessee, Utah, Vermont, Virginia, Washington, and Wisconsin. Concentrations of 5-40 targeted PFAS were analyzed by multiple labs contracted by the states using comparable methods, including either US EPA Method 537, 537.1, or 533. We assigned a conservative, uniform detection limit at the 98th percentile of all reports detection limits (5 ng/L) for the 5 PFAS that were measured in all states consistently. This dataset also incorporates data from the US EPA’s Safe Drinking Water Information System, including the source water type, county served, zip code, system city, and total population served. The 8-digit hydrological unit code in which a CWS intake is estimated to reside is also provided using data from the United States Geological Survey. This was done by geocoding each CWS using geographical data provided by state agencies, reported zip codes (when available), or based on additional information provided by each system (e.g., system name, city, city served). At this time, the full datasets (either system-level or sample-level) are available by request (see contact information below). Note that additional fields, such continuous concentration data, reported detection limits, concentrations of other PFAS analytes, are also available. Proper citation of both this repository and the original associated paper (see recommended citations below) are required for use of these data. Due to the significant time investment required to curate these data, additional data requests beyond the scope of the details listed here are welcomed but should be agreed upon (e.g., in terms of co-authorship) with the primary point of contact. Please contact Jahred Liddie (jliddie@g.harvard.edu) for questions/suggestions, access to additional variables, or access to the full sampling datasets.

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

Furthering the Capabilities of Diffusive-Gradient Passive Samplers for Per- and Polyfluoroalkyl Substances

Abstract. Per- and polyfluoroalkyl substances (PFAS) are chemical pollutants of growing concern for many stakeholders. Due to their ubiquity, persistence i

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 - Chemical and Biological Data from August to September 2018

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.

Field‐testing polyethylene passive samplers for the detection of neutral polyfluorinated alkyl substances in air and water

Abstract . Fluorotelomer alcohols (FTOHs), perfluorooctane‐sulfonamidoethanols (FOSEs), perfluorooctane‐sulfonamides (FOSAs), and other poly‐ and perfluori

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

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

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.

Perfluorinated Carbon Chain Length Drives Uptake of Diverse Per- and Polyfluoroalkyl Substances in Field-Deployed Passive Samplers

Abstract. Per- and polyfluoroalkyl substances (PFAS) are a group of compounds of high concern due to their ubiquity, persistence, and adverse health impact

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

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.

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.