Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases that used aqueous film-forming foams (AFFF) for fire training and firefighting activities. Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods. Here, we estimate the expected duration and contribution of precursor biotransformation to groundwater PFAS contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts, United States, by optimizing a geochemical box model using measured PFAS concentrations from a multidecadal time series of groundwater and a soil survey in the source zone. A toolbox of analytical techniques used to reconstruct the mass budget of PFAS showed that precursors accounted for 46 ± 8% of the extractable organofluorine (a proxy for total PFAS) across years. Terminal PFAS still exceed regulatory limits by 2000-fold decades after AFFF use ceased. Measurements and numerical modeling show that sulfonamido precursors are retained in the vadose zone and their slow biotransformation into perfluoroalkyl sulfonates (half-life > 66 yr) sustains groundwater concentrations of perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS). The estimated PFAS reservoir in the vadose zone and modeled flux into groundwater suggest PFAS contamination above regulatory guidelines will persist for centuries without remediation.

Drinking water supplies across the United States have been contaminated byfirefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much ofthe AFFF ismanufactured using electrochemical fluorination by 3M. Precursors with sixperfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third ofthePFAS in 3M AFFF. C6 precursors can betransformed through nitrification (microbial oxidation) ofamine moieties into perfluorohexane sulfonate (PFHxS), acompound of regulatory concern. Here, wereport biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1−100 pM day⁻¹). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Per- and polyfluoroalkyl substances (PFAS) are a group of 4000+ man-made compounds of great concern due to their environmental ubiquity and adverse effects. Despite general interest, few reliable detection tools for integrative passive sampling of PFAS in water are available. A microporous polyethylene tube with a hydrophilic–lipophilic balance sorbent could serve as a flow-resistant passive sampler for PFAS. The tube’s sampling rate, R_s, was predicted based on either partitioning and diffusion or solely diffusion. At 15 ^°C, the laboratory-measured R_s for perfluorohexanoic acid of 100 ± 81 mL day^–1 was better predicted by a partitioning and diffusion model (48 ± 1.8 mL day^–1) across 10–60 cm s^–1 water flow speeds (15 ± 4.2 mL day^–1 diffusion only). For perfluorohexane sulfonate, R_s at 15 ^°C were similarly different (110 ± 60 mL day^–1 measured, 120 ± 63 versus 12 ± 3.4 mL day^–1 in respective models). R_s values from field deployments were in between these estimates (46 ± 40 mL day^–1 for perfluorohexanoic acid). PFAS uptake was not different for previously biofouled membranes in the laboratory, suggesting the general applicability of the sampler in environmental conditions. This research demonstrates that the polyethylene tube’s sampling rates are sensitive to the parameterization of the models used here and partitioning-derived values should be used.

Per- and polyfluoroalkyl substances (PFAS) are a diverse class of fluorinated anthropogenic chemicals that include perfluoroalkyl acids (PFAA), which are widely used in modern commerce. Many products and environmental samples contain abundant precursors that can degrade into terminal PFAA associated with adverse health effects. Fish consumption is an important dietary exposure source for PFAS that bioaccumulate in food webs. However, little is known about bioaccumulation of PFAA precursors. Here, we identify and quantify PFAS in recreational fish species collected from surface waters across New Hampshire, US, using atoolbox of analytical methods. Targeted analysis of paired water and tissue samples suggests that many precursors below detection in water have ahigher bioaccumulation potential than their terminal PFAA. Perfluorobutane sulfonamide (FBSA), a short-chain precursor produced by electrochemical fluorination, was detected in all fish samples analyzed for this compound. The total oxidizable precursor assay interpreted using Bayesian inference revealed fish muscle tissue contained additional, short-chain precursors in high concentration samples. Suspect screening analysis indicated these were perfluoroalkyl sulfonamide precursors with three and five perfluorinated carbons. Fish consumption advisories are primarily being developed for perfluorooctane sulfonate (PFOS), but this work reinforces the need for risk evaluations to consider additional bioaccumulative PFAS, including perfluoroalkyl sulfonamide precursors.

Drinking water concentrations of per- and polyfluoroalkyl substances (PFAS) exceed provisional guidelines for millions of Americans. Data on private well PFAS concentrations are limited in many regions, and monitoring initiatives are costly and time-consuming. Here, we examine modeling approaches for predicting private wells likely to have detectable PFAS concentrations that could be used to prioritize monitoring initiatives. We used nationally available data on PFAS sources, and geologic, hydrologic and soil properties that affect PFAS transport as predictors, and trained and evaluated models using PFAS data (n ∼ 2300 wells) collected by the state of New Hampshire between 2014 and 2017. Models were developed for the five most frequently detected PFAS: perfluoropentanoate, perfluorohexanoate, perfluoroheptanoate, perfluorooctanoate, and perfluorooctanesulfonate. Classification random forest models that allow nonlinearity in interactions among predictors performed the best (area under the receiver operating characteristics curve: 0.74–0.86). Point sources such as the plastics/rubber and textile industries accounted for the highest contribution to accuracy. Groundwater recharge, precipitation, soil sand content, and hydraulic conductivity were secondary predictors. Our study demonstrates the utility of machine learning models for predicting PFAS in private wells, and the classification random forest model based on nationally available predictors is readily extendable to other regions.

Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary and legacy use of aqueous film forming foams (AFFF) is a major contamination source. However, diverse PFAS sources are present within watersheds, making it difficult to isolate their predominant origins. Here we examine PFAS source signatures among six adjacent coastal watersheds on Cape Cod, MA, U.S.A. using multivariate clustering techniques. A distinct signature of AFFF contamination enriched in precursors with six perfluorinated carbons (C6) was identified in watersheds with an AFFF source, while others were enriched in C4 precursors. Principal component analysis of PFAS composition in impacted watersheds showed a decline in precursor composition relative to AFFF stocks and a corresponding increase in terminal perfluoroalkyl sulfonates with < C6 but not those with ≥ C6. Prior work shows that in AFFF stocks, all extractable organofluorine (EOF) can be explained by targeted PFAS and precursors inferred using Bayesian inference on the total oxidizable precursor assay. Using the same techniques for the first time in impacted watersheds, we find that only 24%–63% of the EOF can be explained by targeted PFAS and oxidizable precursors. Our work thus indicates the presence of large non-AFFF organofluorine sources in these coastal watersheds.

Hundreds of public water systems across the United States have been contaminated by the use of aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS) during firefighting and training activities. Prior work shows AFFF contain hundreds of polyfluoroalkyl precursors missed by standard methods. However, the most abundant precursors in AFFF remain uncertain, and mixture contents are confidential business information, hindering proactive management of PFAS exposure risks. Here, we develop and apply a novel method (Bayesian inference) for reconstructing the fluorinated chain lengths, manufacturing origin, and concentrations of oxidizable precursors obtained from the total oxidizable precursor (TOP) assay that is generally applicable to all aqueous samples. Results show virtually all (median 104 ± 19%) extractable organofluorine (EOF) in contemporary and legacy AFFF consists of targeted compounds and oxidizable precursors, 90% of which are 6:2 fluorotelomers in contemporary products. Using high-resolution mass spectrometry, we further resolved the 6:2 fluorotelomers to assign the identity of 14 major compounds, yielding a priority list that accounts for almost all detectable PFAS in contemporary AFFF. This combination of methods can accurately assign the total PFAS mass attributable to AFFF in any aqueous sample with differentiation of gross precursor classes and identification of major precursor species.

Elevated concentrations of per- and polyfluoroalkyl substances (PFAS) in drinking-water supplies are a major concern for human health. It is therefore essential to understand factors that affect PFAS concentrations in surface water and groundwater and the transformation of perfluoroalkyl acid (PFAA) precursors that degrade into terminal compounds. Surface-water/groundwater exchange can occur along the flow path downgradient from PFAS point sources and biogeochemical conditions can change rapidly at these exchange boundaries. Here, we investigate the influence of surface-water/groundwater boundaries on PFAS transport and transformation. To do this, we conducted an extensive field-based analysis of PFAS concentrations in water and sediment from a flow-through lake fed by contaminated groundwater and its downgradient surface-water/groundwater boundary (defined as ≤100 cm below the lake bottom). PFAA precursors comprised 45 ± 4.6% of PFAS (PFAA precursors + 18 targeted PFAA) in the predominantly oxic lake impacted by a former fire-training area and historical wastewater discharges. In shallow porewater downgradient from the lake, this percentage decreased significantly to 25 ± 11%. PFAA precursor concentrations decreased by 85% between the lake and 84–100 cm below the lake bottom. PFAA concentrations increased significantly within the surface-water/groundwater boundary and in downgradient groundwater during the winter months despite lower stable concentrations in the lake water source. These results suggest that natural biogeochemical fluctuations associated with surface-water/groundwater boundaries may lead to PFAA precursor loss and seasonal variations in PFAA concentrations. Results of this work highlight the importance of dynamic biogeochemical conditions along the hydrological flow path from PFAS point sources to potentially affected drinking water supplies.

This research presents 56 experiments on hydraulic fracturing flowback and produced waters to evaluate common factors affecting electrocoagulation (EC) removal of turbidity, chemical oxygen demand (COD), dissolved organic carbon (DOC) and final pH. Additionally, qualitative reductions in the common fluid additives polyethylene glycols (PEGs) and polypropylene glycols (PPGs), which can interfere with reuse in hydraulic fracturing, were evaluated by mass spectrometry for the first time. Design of experiments tested five EC process control factors: electrode material, current, initial pH, treatment time, and number of electrodes. Turbidity reductions were high (>90 %), and a maximum of 37.4 % of COD and 54.0 % of DOC was removed. Due to low variability, no factors were significant for turbidity reduction, while current, treatment time, and numbers of electrodes were significant factors for COD and DOC reduction. pH increased with iron electrodes and was neutralized with aluminum electrodes. Both PEGs and PPGs were removed, and PPGs were removed to a greater extent. Removal of these compounds increased as they became more hydrophobic as suggested by their logK_ow values. Some analysis was done on removal of common scaling ions (Ba, Ca, Mg, Sr) with removal possibly related to the pH of the water

This study examined water quality, naturally-occurring radioactive materials (NORM), major ions, trace metals, and well flow data for water used and produced from start-up to operation of an oil and gas producing hydraulically-fractured well (horizontal) in the Denver-Julesburg (DJ) Basin in northeastern Colorado. Analysis was conducted on the groundwater used to make the fracturing fluid, the fracturing fluid itself, and nine flowback/produced water samples over 220days of operation. The chemical oxygen demand of the wastewater produced during operation decreased from 8200 to 2500mg/L, while the total dissolved solids (TDS) increased in this same period from 14,200 to roughly 19,000mg/L. NORM, trace metals, and major ion levels were generally correlated with TDS, and were lower than other shale basins (e.g. Marcellus and Bakken). Although at lower levels, the salinity and its origin appear to be the result of a similar mechanism to that of other shale basins when comparing Cl/Br, Na/Br, and Mg/Br ratios. Volumes of returned wastewater were low, with only 3% of the volume injected (11millionliters) returning as flowback by day 15 and 30% returning by day 220. Low levels of TDS indicate a potentially treatment-amenable wastewater, but low volumes of flowback could limit onsite reuse in the DJ Basin. These results offer insight into the temporal water quality changes in the days and months following flowback, along with considerations and implications for water reuse in future hydraulic fracturing or for environmental discharge.