A sensitive method for the detection of legacy and emerging per- and polyfluorinated alkyl substances (PFAS) in dairy milk

There is widespread contamination by per- and polyfluoroalkyl substances (PFAS) across the globe, with adverse effects on human and environmental health. For human exposure, drinking water and dietary exposure have been recognized as important PFAS exposure pathway for the general population. Several documented cases of dairy milk contamination by PFAS have raised concerns over this exposure pathway in general. A sensitive method for determination of 27 PFAS in milk was hence modified and applied on raw and processed milk samples from 13 farms across the United States (U.S.). A combination of acid and basic extraction method and ENVI-Carb clean-up achieved recoveries of targeted PFAS between 70 and 141%. The method detection limits (MDL) ranged from 0.8 to 22 ng/L (for 26 PFAS) and 144 ng/L for perfluorobutanoic acid (PFBA). The uniqueness of this method is considered in the targeted screening of a broad range of legacy PFAS, as well as perfluorinated sulfonamide species and fluorotelomer sulfonates. No legacy PFAS were detected in 13 milk samples from regions of concern given local use of biosolids or proximity to fire training areas. Overall, then, the uptake of perfluoroalkyl acids (PFAA) from dairy milk in the U.S. is considered low

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

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, Rs, was predicted based on either partitioning and diffusion or solely diffusion. At 15 °C, the laboratory-measured Rs 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, Rs at 15 °C were similarly different (110 ± 60 mL day–1 measured, 120 ± 63 versus 12 ± 3.4 mL day–1 in respective models). Rs 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

A graphene-based hydrogel monolith with tailored surface chemistry for PFAS passive sampling

Aquatic contamination by per- and polyfluorinated alkyl substances (PFAS) has attracted global attention due to their environmental and health concerns. Current health advisories and surface water regulatory limits require PFAS detection in the parts per trillion (ppt) range. One way to achieve those low detection limits is to use a reliable passive sampling-based monitoring tool for PFAS, as exists for numerous nonpolar persistent organic pollutants. Here we introduce a new graphene-based hydrogel monolith and describe its synthesis, chemical functionalization, property characterization, and testing as a PFAS equilibrium passive sampler. The graphene monoliths were self-assembled by hydrothermal treatment from graphene oxide (GO) aqueous dispersions to produce free standing cylinders of ∼563 mm3 volume consisting of 4 wt% thin-walled porous graphene and ∼96 wt% water. The uptake of 23 PFAS was measured on the as-produced monoliths, and equilibrium partition coefficients (KSW), were derived for longer chain (C ≥ 8) perfluoroalkyl acids (PFAA) and neutral precursors such as sulfonamides (log KSW range 1.9–3.6). To increase the KSW for shorter chain PFAA, the monoliths were chemically modified by a new diazonium-based grafting reaction that introduces positive surface charge without damage to the graphenic backbone. Introduction of benzylamine moieties through the diazonium intermediate switches zeta potential at pH 7 from −45 mV (as-produced graphene) to +5 mV. This modification increased the sorption of short and middle chain PFAA by ten-fold (e.g. log KSW for PFBA increased from 1.3 to 2.2), thereby improving the functionality of the passive sampler device for a wider range of PFAS. Field deployments demonstrated that the graphene monoliths were capable of detecting key PFAS in the Delaware River

Field validation of a novel passive sampler for dissolved PFAS in surface waters

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

Unregulated Active and Closed Textile Mills Represent a Significant Vector of PFAS Contamination into Coastal Rivers

Despite concerns over the ubiquity of per- and polyfluoroalkyl substances (PFAS), little is known about the diversity of their sources to surface waters and their seasonal dynamics. Frequent use of PFAS in textiles means that both active and closed textile mills require evaluation as PFAS sources. We deployed passive samplers at seven sites in an urban river and estuary adjacent to textile mills in Southern Rhode Island (USA) over 12 months. We estimated monthly mass flows (g month–1) of perfluorohexanoic acid (45 ± 56) and perfluorooctanoic acid (30 ± 45) from the upstream river influenced by an active mill. Average mass flows were 73–155% higher downstream, where historical textile waste lagoons contributed long-chain perfluoroalkyl acids. Mass flows of perfluorononanoic acid increased from 7.5 to 21 g month–1 between the upstream and downstream portions of the rivers. Distinct grouping of the two main PFAS sources, active textile mills and historical waste lagoons, was identified using principal component analysis. Neither suspect screening nor extractable organofluorine analysis revealed that measurable PFASs were missing beyond the targeted compounds. This research demonstrates that both closed and active textile mills are important ongoing PFAS sources to freshwater and marine regions and should be further evaluated as a source category

The Air that we Breathe: Neutral and volatile PFAS in Indoor Air

Sources of exposure to per- and polyfluorinated alkyl substances (PFAS) include food, water, and, given that humans spend typically 90% of their time indoors, air and dust. Quantifying PFAS that are prevalent indoors, such as neutral, volatile PFAS, and estimating their exposure risk to humans are thus important. To accurately measure these compounds indoors, polyethylene (PE) sheets were employed and validated as passive detection tools and analyzed by gas chromatography–mass spectrometry. Air concentrations were compared to dust and carpet concentrations reported elsewhere. Partitioning between PE sheets of different thicknesses suggested that interactions of the PEs with the compounds are occurring by absorption. Volatile PFAS, specifically fluorotelomer alcohols (FTOHs), were ubiquitous in indoor environments. For example, in carpeted Californian kindergarten classrooms, 6:2 FTOH dominated with concentrations ranging from 9 to 600 ng m–3, followed by 8:2 FTOH. Concentrations of volatile PFAS from air, carpet, and dust were closely related to each other, indicating that carpets and dust are major sources of FTOHs in air. Nonetheless, air posed the largest exposure risk of FTOHs and biotransformed perfluorinated alkyl acids (PFAA) in young children. This research highlights inhalation of indoor air as an important exposure pathway and the need for further reduction of precursors to PFAA

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 \u3e kidney \u3e 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;00:1–12. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC

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

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 a toolbox of analytical methods. Targeted analysis of paired water and tissue samples suggests that many precursors below detection in water have a higher 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

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

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L–1 in reference groundwater and 6100 to 15,000 ng L–1 in contaminated groundwater. Biotic concentration factors (CFb) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg–1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CFb generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CFb between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CFb = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CFb, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated

Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report 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 (\u3c1 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