Perfluoroalkyl Sulfonates Research Articles

Critical Evaluation and Meta-Analysis of Ecotoxicological Data on Per- and Polyfluoroalkyl Substances (PFAS) in Freshwater Species.

Despite the increasing concern regarding the ecological risks posed by per- and polyfluoroalkyl substances (PFAS), a lack of comprehensive understanding of their actual ecotoxicity remains. Through a meticulous examination of 91 peer-reviewed studies investigating effects at a population level and constructing probabilistic species sensitivity distributions (PSSDs), we present a state-of-the-science hazard assessment of PFAS in freshwater species. Using data subsets containing suboptimal data led to an overestimation of the predicted no-effect concentrations (PNECs) of PFAS. We report PNECs of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFSAs) in freshwater to be 4.8-2000 μg/L and 0.4-8.9 μg/L, respectively, derived from high-quality data. Statistical analyses revealed that both functional groups and carbon chain length significantly influenced (p < 0.05) the variations in toxicity observed among different PFAS. This study underscores the importance of obtaining high-quality PFAS ecotoxicity data to comprehend associated hazards. The PNECs of PFAS derived in this study are higher compared to those of micro/nanoplastics and persistent organic pollutants. Our research offers valuable insights into prioritizing the regulation of more toxic PFAS.

Neurotoxic Effects of Mixtures of Perfluoroalkyl Substances (PFAS) at Environmental and Human Blood Concentrations.

Per- and polyfluoroalkyl substances (PFAS) may cause various deleterious health effects. Epidemiological studies have demonstrated associations between PFAS exposure and adverse neurodevelopmental outcomes. The cytotoxicity, neurotoxicity, and mitochondrial toxicity of up to 12 PFAS including perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, 6:2 fluorotelomer sulfonic acid (6:2 FTSA), and hexafluoropropylene oxide-dimer acid (HPFO-DA) were tested at concentrations typically observed in the environment (e.g., wastewater, biosolids) and in human blood using high-throughput in vitro assays. The cytotoxicity of all individual PFAS was classified as baseline toxicity, for which prediction models based on partition constants of PFAS between biomembrane lipids and water exist. No inhibition of the mitochondrial membrane potential and activation of oxidative stress response were observed below the cytotoxic concentrations of any PFAS tested. All mixture components and the designed mixtures inhibited the neurite outgrowth in differentiated neuronal cells derived from the SH-SY5Y cell line at concentrations around or below cytotoxicity. All designed mixtures acted according to concentration addition at low effect and concentration levels for cytotoxicity and neurotoxicity. The mixture effects were predictable from the experimental single compounds' concentration-response curves. These findings have important implications for the mixture risk assessment of PFAS.

N-glucuronidation and Excretion of Perfluoroalkyl Sulfonamides in Mice Following Ingestion of Aqueous Film-Forming Foam.

Perfluoroalkyl sulfonamides (FASAs) and other FASA-based per- and polyfluoroalkyl substances (PFASs) can transform into recalcitrant perfluoroalkyl sulfonates in vivo. We conducted high-resolution mass spectrometry suspect screening of urine and tissues (kidney and liver) from mice dosed with an electrochemically fluorinated aqueous film-forming foam (AFFF) to better understand the biological fate of AFFF-associated precursors. The B6C3F1 mice were dosed at five levels (0, 0.05, 0.5, 1, and 5 mg kg-1 day-1) based on perfluorooctane sulfonate and perfluorooctanoate content of the AFFF mixture. Dosing continued for 10 days followed by a 6-day depuration. Total oxidizable precursor assay of the AFFF suggested significant contributions from precursors with three to six perfluorinated carbons. We identified C4 to C6 FASAs and N-glucuronidated FASAs (FASA-N-glus) excreted in urine collected throughout dosing and depuration. Based on normalized relative abundance, FASA-N-glus accounted for up to 33% of the total excreted FASAs in mouse urine, highlighting the importance of phase II metabolic conjugation as a route of excretion. High-resolution mass spectrometry screening of liver and kidney tissue revealed accumulation of longer-chain (C7 and C8) FASAs not detected in urine. Chain-length-dependent conjugation of FASAs was also observed by incubating FASAs with mouse liver S9 fractions. Shorter-chain (C4) FASAs conjugated to a much greater extent over a 120-min incubation than longer-chain (C8) FASAs. Overall, this study highlights the significance of N-glucuronidation as an excretion mechanism for short-chain FASAs and suggests that monitoring urine for FASA-N-glus could contribute to a better understanding of PFAS exposure, as FASAs and their conjugates are often overlooked by traditional biomonitoring studies. Environ Toxicol Chem 2024;43:2274-2284. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

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 > 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.

Fast analysis of short-chain and ultra-short-chain fluorinated organics in water by on-line extraction coupled to HPLC-HRMS

A rapid on-line solid-phase extraction liquid chromatography high-resolution mass spectrometry (on-line SPE-LC-HRMS) method was developed to analyze 11 ultra-short and short-chain PFAS in surface water. Analytical optimization involved screening 7 chromatographic columns and 5 on-line SPE columns, as well as evaluating SPE loading conditions, filters, sample acidification, chromatographic mobile phases, and SPE loading mobile phases. The optimized method was then applied to 44 river water samples collected in Eastern Canada, including sites near airports with fire-training areas. Among the 11 targeted PFAS, the most frequently detected were trifluoroacetic acid (TFA, 4.6–220 ng/L), perfluorobutanoic acid (PFBA, 0.85–33 ng/L), perfluoropentanoic acid (PFPeA, 1.2–2100 ng/L), trifluoromethane sulfonic acid (TMS, 0.01–4.3 ng/L), and perfluorobutane sulfonic acid (PFBS, 0.07–450 ng/L). Levels of C3-C5 perfluoroalkyl carboxylic acids (PFCAs), C2-C4 perfluoroalkyl sulfonates (PFSAs) and n:3 polyfluoroalkyl acids (n = 2,3; n:3 acids) were significantly higher in water bodies near fire-training area sites compared with rivers in urban areas. In contrast, TFA, TMS, and 1:3 acid were not significantly elevated, likely reflecting atmospheric deposition or other diffuse sources for these compounds. Nontarget and suspect screening analysis revealed an abundance of other ultra-short and short-chain PFAS in AFFF-impacted water bodies. Perfluoroalkyl sulfonamides (FASA, C2, C3, and C5), perfluoroalkyl sulfonamide propanoic acids (FASA-PrA, C1-C2) and n:3 acids (n = 1, 4, and 5) were detected for the first time in environmental surface waters.

Nontarget Discovery of Per- and Polyfluoroalkyl Sulfonyl Halides in Soils by Integration of Derivatization and Specific Fragment-Based Liquid Chromatography-High Resolution Mass Spectrometry Screening.

Though long recognized as synthetic precursors to other poly- and perfluoroalkyl substances (PFASs), most poly- and perfluoroalkyl sulfonyl halides (PASXs) cannot be directly measured and have generally received minimal attention. Inspired by the redox reaction between sulfonyl halide groups and p-toluenethiol in organic chemistry, we developed a novel nontarget analysis strategy for PASXs by intergrating derivatization and specific fragment-based liquid chromatography-high resolution mass spectrometry screening for m/z 82.961 [SO2F-] and m/z 95.934 [S2O2-]. By using this strategy, we discovered 11 PASXs, namely, perfluoroalkyl sulfonyl fluorides (5), polyfluoroalkyl sulfonyl fluorides (2), unsaturated perfluoroalkyl sulfonyl fluoride (1), and perfluoroalkyl sulfonyl chlorides (3) in soil samples collected from an abandoned fluorochemical manufacturing park. These average ∑PASXs concentrations were 1120 μg kg-1 (range: 9.7-9860 μg kg-1), which were very likely to be the key intermediates and undesired byproducts of electrochemical fluorination processes. Spatial variation in the mass ratio of ∑PASXs to ∑PFSAs (range: 0.7-795%) also indicates their different transportation pathways. More importantly, the decline of PASXs and increase of perfluoroalkyl sulfonates (when compared to a prior study at this site) suggest the continued hydrolysis of PASXs and the relatively fast environmental transformation rates in the abandoned fluorochemical park soils. Overall, these findings demonstrated the utility of a novel nontarget analysis strategy, which may change most PASXs from inferred precursors to measured intermediates and further could be adapted for structures, distribution, and transformation studies of PFASXs in other matrices.

Overlooked Activation Role of Sulfite in Accelerating Hydrated Electron Treatment of Perfluorosulfonates.

Photoexcitation of sulfite (SO32-) is often used to generate hydrated electrons (eaq-) in processes to degrade perfluoroalkyl and polyfluoroalkyl substances (PFASs). Conventional consensus discourages the utilization of SO32- concentrations exceeding 10 mM for effective defluorination. This has hindered our understanding of SO32- chemistry beyond its electron photogeneration properties. In contrast, the radiation-chemical study presented here, directly producing eaq- through water radiolysis, suggests that SO32- plays a previously overlooked activation role in the defluorination. Quantitative 60Co gamma irradiation experiments indicate that the increased SO32- concentration from 0.1 to 1 M enhances the defluorination rate by a remarkable 15-fold, especially for short-chain perfluoroalkyl sulfonate (PFSA). Furthermore, during the treatment of long-chain PFSA (C8F17-SO3-) with a higher concentration of SO32-, the intermediates of C8H17-SO3- and C3F7-COO- were observed, which are absent without SO32-. These observations highlight that a higher concentration of SO32- facilitates both reaction pathways: chain shortening and H/F exchange. Pulse radiolysis measurements show that elevated SO32- concentrations accelerate the bimolecular reaction between eaq- and PFSA by 2 orders of magnitude. 19F NMR measurements and theoretical simulations reveal the noncovalent interactions between SO32- and F atoms, which exceptionally reduce the C-F bond dissociation energy by nearly 40%. As a result, our study offers a more effective strategy for degrading highly persistent PFSA contaminants.

Perfluoroalkyl sulfonate induces cardiomyocyte apoptosis via endoplasmic reticulum stress activation and autophagy flux inhibition

Perfluoroalkyl sulfonate (PFOS) is a commonly used chemical compound that often found in materials such as waterproofing agents, food packaging, and fire retardants. Known for its stability and persistence in the environment, PFOS can enter the human body through various pathways, including water and the food chain, raising concerns about its potential harm to human health. Previous studies have suggested a cardiac toxicity of PFOS, but the specific cellular mechanisms remained unclear. Here, by using AC16 cardiomyocyte as a model to investigate the molecular mechanisms potential the cardiac toxicity of PFOS. Our findings revealed that PFOS exposure reduced cell viability and induces apoptosis in human cardiomyocyte. Proteomic analysis and molecular biological techniques showed that the Endoplasmic Reticulum (ER) stress-related pathways were activated, while the cellular autophagy flux was inhibited in PFOS-exposed cells. Subsequently, we employed strategies such as autophagy activation and ER stress inhibition to alleviate the PFOS-induced apoptosis in AC16 cells. These results collectively suggest that PFOS-induced ER stress activation and autophagy flux inhibition contribute to cardiomyocyte apoptosis, providing new insights into the mechanisms of PFOS-induced cardiomyocyte toxicity.

Retention of per- and polyfluoroalkyl substances by syringe filters

Per- and polyfluoroalkyl substances (PFAS) are being increasingly measured in water and wastewater due to emerging toxicity concerns and strict regulatory limits. Previous studies have filtered water samples to remove suspended solids before PFAS analysis. However, filtration may introduce negative bias to measured PFAS concentrations. Using a well-controlled syringe pump assembly, we evaluated retention of six perfluoroalkyl carboxylates, three perfluoroalkyl sulfonates, one fluorotelomer sulfonate, and two perfluorooctane sulfonamides by glass-fiber, glass-fiber cellulose acetate, nylon, polyethersulfone, polypropylene, polyvinylidene fluoride/ difluoride, and surfactant-free cellulose acetate filters. The impacts of water quality and operational parameters were also investigated for select filter types. We found that PFAS were retained on all filters, with the glass-fiber cellulose acetate filters demonstrating the lowest retention. For all filters, PFAS retention was linearly related to chain length and hydrophobicity above certain thresholds (i.e., log D higher than 1.5). Importantly, more PFAS were retained at low filtrate volumes, and ~ 30 mL filtrate was required before the retention efficiencies stabilized. Solution pH only affected the retention of perfluorooctane sulfonamides. Pore size (i.e., 0.20, 0.45, 0.70 µm), filtration rate (i.e., 0.5, 1.0 mL min−1), and PFAS concentration (i.e., 10, 100 µg L−1), did not exert major influences on PFAS retention. The presence of dissolved organic matter improved PFAS permeation. Based on the reported results, filtration introduces bias and is not recommended for sample pretreatment.

Application of electron beam technology to decompose per- and polyfluoroalkyl substances in water

The widespread detection of per- and polyfluoroalkyl substances (PFAS) in environmental compartments across the globe has raised several health concerns. Destructive technologies that aim to transform these recalcitrant PFAS into less toxic, more manageable products, are gaining impetus to address this problem. In this study, a 9 MeV electron beam accelerator was utilized to treat a suite of PFAS (perfluoroalkyl carboxylates: PFCAs, perfluoroalkyl sulfonates, and 6:2 fluorotelomer sulfonate: FTS) at environmentally relevant levels in water under different operating and water quality conditions. Although perfluorooctanoic acid and perfluorooctane sulfonic acid showed >90% degradation at <500 kGy dose at optimized conditions, a fluoride mass balance revealed that complete defluorination occurred only at/or near 1000 kGy. Non-target and suspect screening revealed additional degradation pathways differing from previously reported mechanisms. Treatment of PFAS mixtures in deionized water and groundwater matrices showed that FTS was preferentially degraded (∼90%), followed by partial degradation of long-chain PFAS (∼15–60%) and a simultaneous increase of short-chain PFAS (up to 20%) with increasing doses. The increase was much higher (up to 3.5X) in groundwaters compared to deionized water due to the presence of PFAS precursors as confirmed by total oxidizable precursor (TOP) assay. TOP assay of e-beam treated samples did not show any increase in PFCAs, confirming that e-beam was effective in also degrading precursors. This study provides an improved understanding of the mechanism of PFAS degradation and revealed that short-chain PFAS are more resistant to defluorination and their levels and regulation in the environment will determine the operating conditions of e-beam and other PFAS treatment technologies.

Bioaccumulation of Perfluoroalkyl Sulfonamides (FASA).

Hundreds of sites across the United States have high concentrations of perfluoroalkyl sulfonamides (FASA), but little is known about their propensity to accumulate in fish. FASA are precursors to terminal per- and polyfluoroalkyl substances (PFAS) that are abundant in diverse consumer products and aqueous film-forming foams manufactured using electrochemical fluorination (ECF AFFF). In this study, FASA with C3-C8 carbon chain lengths were detected in all fish samples from surface waters up to 8 km downstream of source zones with ECF AFFF contamination. Short-chain FASA ≤ C6 have rarely been included in routine screening for PFAS, but availability of new standards makes such analyses more feasible. Bioaccumulation factors (BAF) for FASA were between 1 and 3 orders of magnitude greater than their terminal perfluoroalkyl sulfonates. Across fish species, BAF for FASA were greater than for perfluorooctanesulfonate (PFOS), which is presently the focus of national advisory programs. Similar concentrations of the C6 FASA (<0.36-175 ng g-1) and PFOS (0.65-222 ng g-1) were detected in all fish species. No safety thresholds have been established for FASA. However, high concentrations in fish next to contaminated sites and preliminary findings on toxicity suggest an urgent need for consideration by fish advisory programs.

Concentrations of 45 Per- and Polyfluoroalkyl Substances in North American River Otters (Lontra canadensis) from West Virginia, USA.

North American river otters (Lontra canadensis) are top predators in riverine ecosystems and are vulnerable to per- and polyfluoroalkyl substance (PFAS) exposure. Little is known about the magnitude of exposure and tissue distribution of PFAS in river otters. We measured 45 PFAS in various tissues of 42 river otters collected from several watersheds in the state of West Virginia, USA. The median concentrations of ∑All (sum concentration of 45 PFAS) varied among tissues in the following decreasing order: liver (931 ng/g wet weight) > bile > pancreas > lung > kidney > blood > brain > muscle. Perfluoroalkylsulfonates (PFSAs) were the predominant compounds accounting for 58-75% of the total concentrations, followed by perfluoroalkyl carboxylates (PFCAs; 21-35%). 8:2 fluorotelomer sulfonate (8:2 FTS), 10:2 FTS, and 6:2 chlorinated polyfluoroalkyl ether sulfonate were frequently found in the liver (50-90%) and bile (96-100%), whereas hexafluoropropylene oxide dimer acid (HFPO-DA) was rarely found. The hepatic concentrations of ∑All in river otters collected downstream of a fluoropolymer production facility located along the Ohio River were 2-fold higher than those in other watersheds. The median whole body burden of ∑All was calculated to be 1580 μg. PFOS and perfluorooctanoic acid (PFOA) concentrations in whole blood of some river otters exceeded the human toxicity reference values, which warrant further studies.

Determination of perfluorinated compounds in Eichhornia crassipes (Mart.) Solms using LC-MS/MS in combination with sample preparation by ultrasound-assisted extraction and solid-phase extraction

Fifteen perfluorinated compounds, including perfluorocarboxylic acids and perfluoroalkyl sulfonate salts (with 4 to 12 carbon atoms in their structure) in Eichhornia crassipes (Mart.) Solms samples underwent analysis using Liquid Chromatography- tandem Mass Spectrometry (LC-MS/MS). This analysis was conducted alongside sample preparation employing ultrasound-assisted extraction and solid-phase extraction. The optimization of solvent extraction involved the use of 5 ml of methyl tert-butyl ether (MTBE), 10 minutes of sonication, and three repeated extraction cycles. The weak anion exchange (WAX) cartridge was selected after evaluating and comparing the solid-phase extraction efficiencies of both WAX and C18 cartridges. The evaluated method demonstrated successful analysis of all 15 PFCs in plant samples, achieving favorable recoveries ranging from 71 to 116% (with a coefficient of variation of 1.2-6.6%). The quantification limits for these 15 PFCs in Eichhornia crassipes (Mart.) Solms samples ranged between 0.30 to 0.54 ng/g.&#x0D; ® 2023 Journal of Science and Technology - NTTU

Hydrothermal Alkaline Treatment (HALT) of Foam Fractionation Concentrate Derived from PFAS-Contaminated Groundwater.

While foam fractionation (FF) process has emerged as a promising technology for removal of per- and polyfluoroalkyl substances (PFASs) from contaminated groundwater, management of the resulting foam concentrates with elevated concentrations of PFASs (e.g., >1 g/L) remains a challenge. Here, we applied hydrothermal alkaline treatment (HALT) to two foam concentrates derived from FF field demonstration projects that treated aqueous film-forming foam (AFFF)-impacted groundwater. Results showed >90% degradation and defluorination within 90 min of treatment (350 °C, 1 M NaOH) of all 62 PFASs (including cations, anions, and zwitterions) identified in foam concentrates. Observed rate constants for degradation of individual perfluoroalkyl sulfonates (PFSAs, CnF2n+1-SO3-), the most recalcitrant class of PFASs, in both foam concentrates were similar to values measured previously in other aqueous matrices, indicating that elevated initial PFAS concentrations (e.g., PFHxSinit = 0.55 g/L), dissolved organic carbon (DOC; up to 4.5 g/L), and salt levels (e.g., up to 325 mg/L chloride) do not significantly affect PFAS reaction kinetics. DOC was partially mineralized by treatment, but a fraction (∼15%) was recalcitrant. Spectroscopic characterization revealed molecular features of the HALT-recalcitrant DOC fraction, and nontarget high-resolution mass spectrometry tentatively identified 129 nonfluorinated HALT-recalcitrant molecules. Analysis of process energy requirements shows that treating PFAS-contaminated foam concentrates with HALT would add minimally (<5%) to the overall energy requirements of an integrated FF-HALT treatment train.

Environmental distribution of per- and polyfluoroalkyl substances (PFAS) on Svalbard: Local sources and long-range transport to the Arctic

The environmental distribution of per- and polyfluoroalkyl substances (PFAS) in water, snow, sediment and soil samples taken along the west coast of Spitsbergen in the Svalbard archipelago, Norwegian Arctic, was determined. The contribution of potential local primary sources (wastewater, firefighting training site at Svalbard airport, landfill) to PFAS concentrations and long-range transport (atmosphere, ocean currents) were then compared, based on measured PFAS levels and composition profiles. In remote coastal and inland areas of Spitsbergen, meltwater had the highest mean ΣPFAS concentration (6.5 ± 1.3 ng L−1), followed by surface snow (2.5 ± 1.7 ng L−1), freshwater (2.3 ± 1.1 ng L−1), seawater (1.05 ± 0.64 ng L−1), lake sediments (0.084 ± 0.038 ng g−1 dry weight (dw)) and marine sediments (<method detection limit (MDL)–0.46 ng g−1 dw, median 0.015 ng g−1 dw). Perfluoroalkyl sulfonates (PFSA) and 6:2 fluorotelomer sulfonate (FTSA) were predominant in water and soil samples influenced by local sources, while perfluoroalkyl carboxylates (PFCA) were predominant in water and sediment from remote coastal and inland areas of Svalbard. The PFAS composition profiles observed in remote areas indicated that atmospheric transport and oxidation of volatile precursors is an important source of PFCA on Svalbard. Shorter-chain PFAS such as perfluorobutanoate (PFBA) were the predominant PFAS in freshwater, reflecting replacement of C8-chained PFAS with shorter-chained compounds. The comparatively high PFAS (especially PFBA) concentration in meltwater indicated that melting of snow and ice during the Arctic spring is an important diffuse local PFAS source. This source may become even more important with climate warming-induced melting of Arctic glaciers and ice sheets. Further studies of mobilisation and transport of PFAS in the Arctic region are needed to confirm this trend.

Inputs, amplification and sinks of perfluoroalkyl substances at coastal Antarctica

The sources, biogeochemical controls and sinks of perfluoroalkyl substances, such as perfluoroalkyl acids (PFAAs), in polar coastal regions are largely unknown. These were evaluated by measuring a large multi-compartment dataset of PFAAs concentrations at coastal Livingston and Deception Islands (maritime Antarctica) during three austral summers. PFAAs were abundant in atmospheric-derived samples (aerosols, rain, snow), consistent with the importance of atmospheric deposition as an input of PFAAs to Antarctica. Such PFAAs deposition was unequivocally demonstrated by the occurrence of PFAAs in small Antarctic lakes. Several lines of evidence supported the relevant amplification of PFAAs concentrations in surface waters driven by snow scavenging of sea-spray aerosol-bound PFAAs followed by snow-melting. For example, vertical profiles showed higher PFAAs concentrations at lower-salinity surface seawaters, and PFAAs concentrations in snow were significantly higher than in seawater. The higher levels of PFAAs at Deception Island than at Livingston Island are consistent with the semi-enclosed nature of the bay. Concentrations of PFOS decreased from 2014 to 2018, consistent with observations in other oceans. The sink of PFAAs due to the biological pump, transfer to the food web, and losses due to sea-spray aerosols alone are unlikely to have driven the decrease in PFOS concentrations. An exploratory assessment of the potential sinks of PFAAs suggests that microbial degradation of perfluoroalkyl sulfonates should be a research priority for the evaluation of PFAAs persistence in the coming decade.

Presence of Perfluoroalkyl Carboxylic Acids and Sulfonates in Vietnamese Food Contact Materials

Per- and polyfluoroalkyl substances (PFASs) are considered as persistent organic pollutants (POPs), which should be restricted or eliminated. In this study, concentrations of four perfluoroalkyl carboxylic acids (perfluorobutanoic acid PFBA, perfluorohexanoic acid PFHxA, perfluorooctanoic acid PFOA, perfluorodecanoic acid PFDA) and four perfluoroalkyl sulfonates (perfluorobutane sulfonate PFBS, perfluorohexane sulfonate PFHxS, perfluorooctane sulfonate PFOS, perfluorodecane sulfonate PFDS) were analyzed in food contact materials (FCM) collected from Hanoi, Vietnam. A total of 15 FCM samples was obtained including several categories such as instant drink/food boxes, bags, cups, wrappers, and tray. The FCM samples were untrasonic extracted with methanol, concentrated, and filtered before analysis by a liquid chromatography–tandem mass spectrometry (LC-MS/MS) system. Recoveries of native and surrogate standards ranged from 70% to 130% with RSD &lt; 20% in replicated analysis. Method detection limits of PFASs ranged from 0.04 to 0.08 ng/g. Concentrations of S8PFASs ranged from not detected (ND) to 1.46 (average ± SD: 0.417 ± 0.479) ng/g. Detection frequencies of PFASs decreased in the order: PFDA (33%) &gt; PFBA, PFOA, PFHxS, PFOS (27%) &gt; PFDS (13%) &gt; PFHxA (7%) &gt; PFBS (0%). Average concentrations of individual compounds decreased in the order: PFOS &gt; PFDA &gt; PFHxS &gt; PFOA &gt; PFBA &gt; PFHxA &gt; PFDS &gt; PFBS. Relatively low PFAS concentrations found in the FCM samples of this study indicated that these substances were mainly derived from unintentional sources rather than intentionally added to the materials.&#x0D;

Using 19F NMR to Investigate Cationic Carbon Dot Association with Per- and Polyfluoroalkyl Substances (PFAS).

There is much concern about per- and polyfluoroalkyl substances (PFAS) based on their environmental persistence and toxicity, resulting in an urgent need for remediation technologies. This study focused on determining if nanoscale polymeric carbon dots are a viable sorbent material for PFAS and developing fluorine nuclear magnetic resonance spectroscopy (19F NMR) methods to probe interactions between carbon dots and PFAS at the molecular scale. Positively charged carbon dots (PEI-CDs) were synthesized using branched polyethyleneimine to target anionic PFAS by promoting electrostatic interactions. PEI-CDs were exposed to perfluorooctanoic acid (PFOA) to assess their potential as a PFAS sorbent material. After exposure to PFOA, the average size of the PEI-CDs increased (1.6 ± 0.5 to 7.8 ± 1.8 nm) and the surface charge decreased (+38.6 ± 1.1 to +26.4 ± 0.8 mV), both of which are consistent with contaminant sorption. 19F NMR methods were developed to gain further insight into PEI-CD affinity toward PFAS without any complex sample preparation. Changes in PFOA peak intensity and chemical shift were monitored at various PEI-CD concentrations to establish binding curves and determine the chemical exchange regime. 19F NMR spectral analysis indicates slow-intermediate chemical exchange between PFOA and CDs, demonstrating a high-affinity interaction. The α-fluorine had the greatest change in chemical shift and highest affinity, suggesting electrostatic interactions are the dominant sorption mechanism. PEI-CDs demonstrated affinity for a wide range of analytes when exposed to a mixture of 24-PFAS, with a slight preference toward perfluoroalkyl sulfonates. Overall, this study shows that PEI-CDs are an effective PFAS sorbent material and establishes 19F NMR as a suitable method to screen for novel sorbent materials and elucidate interaction mechanisms.

Perfluoroalkyl Substances in Seabird Eggs from Canada's Pacific Coast: Temporal Trends (1973-2019) and Interspecific Patterns.

Whether perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) are responding to legislative restrictions and showing decreasing trends in top marine predators that range across the eastern North Pacific Ocean is unclear. Here, we examined longer-term temporal trends (1973-2019) of 4 PFSAs and 13 PFCAs, as well stable isotopes of δ13C and δ15N, in the eggs of 4 seabird species sampled along a nearshore-offshore gradient; double-crested cormorants (Nannopterum auritum), pelagic cormorants (Urile pelagicus), rhinoceros auklets (Cerorhinca monocerata), and Leach's storm-petrels (Hydrobates leucorhous) from the Pacific coast of British Columbia, Canada. PFOS was the most abundant PFSA (79-94%) detected in all eggs regardless of colony and year, with the highest concentrations, on average, measured in auklet eggs (mean = 58 ng g-1, range = 11-286 ng g-1 ww). Perfluoroundecanoic acid (PFUdA) and perfluorotridecanoic acid (PFTriDA) were the dominant long-chain PFCAs (≥30% combined). The majority of PFSAs (including PFOS) are statistically declining (p < 0.001) in the eggs of all 4 species with PFOS half-lives ranging from 2.6 to 7.8 years. Concentrations of long-chain PFCAs exhibited a trajectory comprised of linear increases and second-order declines, suggesting that the rate of uptake of PFCAs is slowing or leveling off. These trends are consistent with the voluntarily ceased production of PFSAs by 3M circa 2000-2003 and are among the first from the northeast Pacific to indicate a positive response to several regulations and restrictions on PFCAs from facility emissions and product content.

Mass flow of per- and polyfluoroalkyl substances (PFAS) in a Swedish municipal wastewater network and wastewater treatment plant

Perand polyfluoroalkyl substances (PFAS) are ubiquitously distributed in wastewater, due to their numerous uses in industry and consumer products, but little is known of PFAS mass flows in municipal wastewater network systems and within wastewater treatment plants (WWTPs). This study assessed mass flows of 26 PFAS in a wastewater network and WWTP, to provide new insights into their sources, transport, and fate in different treatment steps. Wastewater and sludge samples were collected from pumping stations and the main WWTP in Uppsala, Sweden. PFAS composition profiles and mass flows were used to identify sources within the sewage network. Wastewater from one pumping station showed elevated concentrations of C3–C8 PFCA, likely caused by an industrial source, and two stations had elevated concentrations of 6:2 FTSA, probably originating from a nearby firefighter training facility. Within the WWTP, short-chain PFAS dominated in wastewater, whereas long-chain PFAS dominated in sludge. The ratio of perfluoroalkyl sulfonates (PFSA) and ethylperfluorooctanesulfonamidoacetic acid (EtFOSAA) to ∑26PFAS decreased during the WWTP process, likely due to sorption to sludge, but also transformation (EtFOSAA). Overall, PFAS were not efficiently removed in the WWTP, with mean removal efficiency of 10 ± 68% for individual PFAS, resulting in discharge of 7000 mg d−1 ∑26PFAS into the recipient. This shows that conventional WWTPs are inefficient in removing PFAS from wastewater and sludge, so advanced treatment techniques are needed.