Fluorotelomer Carboxylic Acid Research Articles

The Transformation of Per- and Polyfluoroalkyl Substances in the Aquatic Environment of a Fluorochemical Industrial Park

Jiangsu High-Tech Fluorochemical Industrial Park in Changshu City, Jiangsu Province, is the largest fluorochemical industrial park in Asia. The occurrence of per- and polyfluoroalkyl substances (PFASs) in surface water and widespread local plants was investigated in Jiangsu High-Tech Fluorochemical Industrial Park. Thirty-two target PFASs were detected in dissolved-phase, particle-phase and plant samples. The concentrations of total PFASs ranged from 1650 to 8250 ng/L in the dissolved-phase samples, 132 to 6810 ng/g dw in the particle-phase samples and 25.8 to 9460 ng/g dw in different plant tissues. Perfluorohexanoic acid (PFHxA), Perfluorooctanoate acid (PFOA) and 6:2 fluorotelomer carboxylic acid (6:2 FTCA) were predominant PFASs and contributed 80−91% to ΣPFAS in water samples. A total of 67 emerging PFAS were identified in all samples using nontargeted analysis. Typha orientalis showed better accumulation ability, with an average ΣPFAS concentration of 3450 ng/g dw and the highest root concentration factor (RCF) of 171. Typha orientalis, Eichhornia crassipes and Alternanthera sessilis have potential for use in PFAS phytostabilization.

Investigating the sources and fate of per- and polyfluoroalkyl substances (PFAS) in food waste compost

Composting municipal food waste is a key strategy for beneficially reusing methane-producing waste that would otherwise occupy landfill space. However, land-applied compost can cycle per- and polyfluoroalkyl substances (PFAS) back into the food supply and the environment. We partnered with a pilot-scale windrow composting facility to investigate the sources and fate of 40 PFAS in food waste compost. A comparison of feedstock materials yielded concentrations of ∑PFAS under 1 ng g−1 in mulch and food waste and at 1380 ng g−1 in leachate from used compostable food contact materials. Concentrations of targeted ∑PFAS increased with compost maturity along the windrow (1.85–23.1 ng g−1) and in mature stockpiles of increasing curing age (12.6–84.3 ng g−1). Among 15 PFAS quantified in compost, short-chain perfluorocarboxylic acids (PFCAs) – C5 and C6 PFCAs in particular – led the increasing trend, suggesting biotransformation of precursor PFAS into these terminal PFAS through aerobic decomposition. Several precursor PFAS were also measured, including fluorotelomer carboxylic acids (FTCAs) and polyfluorinated phosphate diesters (PAPs). However, since most targeted analytical methods and proposed regulations prioritize terminal PFAS, testing fully matured compost would provide the most relevant snapshot of PFAS that could be land applied. In addition, removing co-disposed food contact materials from the FW feedstock onsite yielded only a 37 % reduction of PFAS loads in subsequent compost, likely due to PFAS leaching during co-disposal. Source-separation of food contact materials is currently the best management practice for meaningful reduction of PFAS in food waste composts intended for land application.

Distinctive biotransformation and biodefluorination of 6:2 versus 5:3 fluorotelomer carboxylic acids by municipal activated sludge

Fluorotelomer carboxylic acids (FTCAs) represent an important group of per- and polyfluoroalkyl substances (PFAS) given their high toxicity, bioaccumulation potential, and frequent detection in landfill leachates and PFAS-impacted sites. In this study, we assessed the biodegradability of 6:2 FTCA and 5:3 FTCA by activated sludges from four municipal wastewater treatment plants (WWTPs) in the New York Metropolitan area. Coupling with 6:2 FTCA removal, significant fluoride release (0.56∼1.83 F-/molecule) was evident in sludge treatments during 7 days of incubation. Less-fluorinated transformation products (TPs) were formed, including 6:2 fluorotelomer unsaturated carboxylic acid (6:2 FTUCA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), and perfluorobutanoic acid (PFBA). In contrast, little fluoride (0.01∼0.09 F-/molecule) was detected in 5:3 FTCA-dosed microcosms, though 25∼68% of initially dosed 5:3 FTCA was biologically removed. This implies the dominance of “non-fluoride-releasing pathways” that may contribute to the formation of CoA adducts or other conjugates over 5:3 FTCA biotransformation. The discovery of defluorinated 5:3 FTUCA revealed the possibility of microbial attacks of the C-F bond at the γ carbon to initiate the transformation. Microbial community analysis revealed the possible involvement of 9 genera, such as Hyphomicrobium and Dechloromonas, in aerobic FTCA biotransformation. This study unraveled that biotransformation pathways of 6:2 and 5:3 FTCAs can be divergent, resulting in biodefluorination at distinctive degrees. Further research is underscored to uncover the nontarget TPs and investigate the involved biotransformation and biodefluorination mechanisms and molecular basis.

Suspect, Nontarget Screening, and Toxicity Prediction of Per- and Polyfluoroalkyl Substances in the Landfill Leachate.

Landfills are the final stage of urban wastes containing perfluoroalkyl and polyfluoroalkyl substances (PFASs). PFASs in the landfill leachate may contaminate the surrounding groundwater. As major environmental pollutants, emerging PFASs have raised global concern. Besides the widely reported legacy PFASs, the distribution and potential toxic effects of numerous emerging PFASs remain unclear, and unknown PFASs still need discovery and characterization. This study proposed a comprehensive method for PFAS screening in leachate samples using suspect and nontarget analysis. A total of 48 PFASs from 10 classes were identified; nine novel PFASs including eight chloroperfluoropolyether carboxylates (Cl-PFPECAs) and bistriflimide (HNTf2) were reported for the first time in the leachate, where Cl-PFPECA-3,1 and Cl-PFPECA-2,2 were first reported in environmental media. Optimized molecular docking models were established for prioritizing the PFASs with potential activity against peroxisome proliferator-activated receptor α and estrogen receptor α. Our results indicated that several emerging PFASs of N-methyl perfluoroalkyl sulfonamido acetic acids (N-MeFASAAs), n:3 fluorotelomer carboxylic acid (n:3 FTCA), and n:2 fluorotelomer sulfonate (n:2 FTSA) have potential health risks that cannot be ignored.

Removal of per- and polyfluoroalkyl substances from wastewater via aerosol capture

The widespread use of per- and polyfluoroalkyl substances (PFAS)-containing products in numerous commercial and industrial applications has resulted in their occurrence in wastewater treatment plants (WWTPs). Herein, proof-of-concept bench-scale experiments were performed to measure the extent to which PFAS could be removed from a WWTP if aerosols generated during aeration were captured. Experiments were designed to mimic the aeration rate:water volume ratio, the water volume:surface area ratio, and aeration bubble size applicable to the full-scale aeration vessel. Results showed that substantial (75%) removal of perfluorooctane sulfonate (PFOS) was observed under these operating conditions in the bench-scale system; up to 97% PFOS removal was observed if the aeration rate was increased 3-fold. PFAS removal generally increased with increasing aerosol capture and with increasing PFAS surface activity. Analysis of semi-quantified PFAS showed that the semi-quantified PFAS accounted for approximately 93% of the identified PFAS in the raw wastewater, dominated largely by the presence of 2:2 fluorotelomer carboxylic acid (2:2 FTCA). This preliminary study suggests that aerosol capture in aeration basins has potential for mitigating PFAS in WWTPs. Further testing is needed to assess the feasibility of this approach at the field scale.

Structural dependence of PFAS oxidation in a boron doped diamond-electrochemical system

Driven by long-term persistence and adverse health impacts of legacy perfluorooctanoic acid (PFOA), production has shifted towards shorter chain analogs (C4, perfluorobutanoic acid (PFBA)) or fluorinated alternatives such as hexafluoropropylene oxide dimer acid (HFPO-DA, known as GenX) and 6:2 fluorotelomer carboxylic acid (6:2 FTCA). Yet, a thorough understanding of treatment processes for these alternatives is limited. Herein, we conducted a comprehensive study using an electrochemical approach with a boron doped diamond anode in Na2SO4 electrolyte for the remediation of PFOA common alternatives, i.e., PFBA, GenX, and 6:2 FTCA. The degradability, fluorine recovery, transformation pathway, and contributions from electro-synthesized radicals were investigated. The results indicated the significance of chain length and structure, with shorter chains being harder to break down (PFBA (65.6 ± 5.0%) < GenX (84.9 ± 3.3%) < PFOA (97.9 ± 0.1%) < 6:2 FTCA (99.4 ± 0.0%) within 120 min of electrolysis). The same by-products were observed during the oxidation of both low and high concentrations of parent PFAS (2 and 20 mg L−1), indicating that the fundamental mechanism of PFAS degradation remained consistent. Nevertheless, the ratio of these by-products to the parent PFAS concentration varied which primarily arises from the more rapid PFAS decomposition at lower dosages. For all experiments, the main mechanism of PFAS oxidation was initiated by direct electron transfer at the anode surface. Sulfate radical (SO4•−) also contributed to the oxidation of all PFAS, while hydroxyl radical (•OH) only played a role in the decomposition of 6:2 FTCA. Total fluorine recovery of PFBA, GenX, and 6:2 FTCA were 96.5%, 94.0%, and 76.4% within 240 min. The more complex transformation pathway of 6:2 FTCA could explain its lower fluorine recovery. Detailed decomposition pathways for each PFAS were also proposed through identifying the generated intermediates and fluorine recovery. The proposed pathways were also assessed using 19F Nuclear Magnetic Resonance (NMR) spectroscopy.

Evaluating the toxicokinetics of some metabolites of a C6 polyfluorinated compound, 6:2 fluorotelomer alcohol in pregnant and nonpregnant rats after oral exposure to the parent compound

The 6:2 fluorotelomer alcohol (6:2 FTOH) is a common impurity in per- and polyfluoroalkyl substances (PFASs) used in many applications. Our previous toxicokinetic (TK) evaluation of 6:2 FTOH calculated times to steady state (tss) of one of its metabolites, 5:3 fluorotelomer carboxylic acid (5:3A), in the plasma and tissues of up to a year after oral exposure to rats. Our current work further elucidated the TK of 5:3A and other metabolites of 6:2 FTOH in pregnant and nonpregnant rats after repeated oral exposure and examined the role of renal transporters in the biopersistence of 5:3A. The tss values for 5:3A in serum and tissues of adult nonpregnant animals ranged from 150 days to over a year. 4:3 fluorotelomer carboxylic acid (4:3A) was an additional potentially-biopersistent metabolite. 5:3A was the major metabolite of 6:2 FTOH in serum of pregnant dams and fetuses at each time interval. 5:3A was not a substrate for renal transporters in a human kidney cell line in vitro, indicating that renal reuptake of 5:3A is unlikely contribute to its biopersistence. Further research is needed to identify the underlying processes and evaluate the impact of these 6:2 FTOH metabolites on human health.

Microfluidic Chip-Based Modeling of Three-Dimensional Intestine-Vessel-Liver Interactions in Fluorotelomer Alcohol Biotransformation.

Plyfluoroalkyl substance (PFAS), featured with incredible persistence and chronic toxicity, poses an emerging ecological and environmental crisis. Although significant progress has been made in PFAS metabolism in vivo, the underlying mechanism of metabolically active organ interactions in PFAS bioaccumulation remains largely unknown. We developed a microfluidic-based assay to recreate the intestine-vessel-liver interface in three dimensions, allowing for high-resolution, real-time images and precise quantification of intestine-vessel-liver interactions in PFAS biotransformation. In contrast to the scattered arrangement of vascular endothelium on the traditional d-polylysine-modified two-dimensional (2D) plate, the microtubules in our three-dimensional (3D) platform formed a dense honeycomb network through the ECM, with longer tubular structures. Additionally, the slope culture of epithelial cells in our platform exhibited a closely arranged and thicker cell layer than the planar culture. To dynamically monitor the metabolic crosstalk in the intestinal-vascular endothelium-liver interaction under exposure to fluorotelomer alcohols (FTOHs), we combined the chip with a solid-phase extraction-mass spectrometry (SPE-MS) system. Our findings revealed that endothelial cells were involved in the metabolic process of FTOHs. The transformation of intestinal epithelial and hepatic epithelial cells produces toxic metabolite fluorotelomer carboxylic acids (FTCAs), which circulate to endothelial cells and affect angiogenesis. This system shows promise as an enhanced surrogate model and platform for studying pollutant exposure as well as for biomedical and pharmaceutical research.

Using regular and transcriptomic analyses to investigate the biotransformation mechanism and phytotoxic effects of 6:2 fluorotelomer carboxylic acid (6:2 FTCA) in pumpkin (Cucurbita maxima L.)

Although 6:2 fluorotelomer carboxylic acid (6:2 FTCA), which is one of the most popular substitutes for perfluorooctanoic acid (PFOA), has been widely distributed in environments, little is known about its biotransformation mechanism and phytotoxic effects in plants. Here, we showed that 6:2 FTCA could be taken up by pumpkin (Cucurbita maxima L.) roots from exposure solution and acropetally translocated to shoots. Biotransformation of 6:2 FTCA to different carbon chain perfluorocarboxylic acid (PFCA) metabolites (C2-C7) via α-and β-oxidation in pumpkin was observed, and perfluorohexanoic acid (PFHxA) was the major transformation product. The results of enzyme assays, enzyme inhibition experiments and gene expression analysis indicated that cytochrome P450 (CYP450), glutathione-S-transferase (GST) and ATP-binding cassette (ABC) transporters were involved in the metabolism of 6:2 FTCA in pumpkin. Plant-associated rhizobacteria and endophyte also contributed to 6:2 FTCA degradation through β-oxidation. The chlorophyll (Chl) content and genes involved in photosynthesis were significantly improved by 6:2 FTCA. The reductions of antioxidant and metabolic enzyme activities reflected the antioxidant defense system and detoxification system of pumpkin were both damaged, which were further confirmed by the down-regulating associated genes encoding phenylpropanoid biosynthesis, endoplasmic reticulum-related proteins, ascorbate-glutathione cycle and ABC transporters. This study is helpful to understand the environmental behaviors and toxicological molecular mechanisms of 6:2 FTCA in plants.

Target and Suspect Screening Integrated with Machine Learning to Discover Per- and Polyfluoroalkyl Substance Source Fingerprints.

This study elucidates per- and polyfluoroalkyl substance (PFAS) fingerprints for specific PFAS source types. Ninety-two samples were collected from aqueous film-forming foam impacted groundwater (AFFF-GW), landfill leachate, biosolids leachate, municipal wastewater treatment plant effluent (WWTP), and wastewater effluent from the pulp and paper and power generation industries. High-resolution mass spectrometry operated with electrospray ionization in negative mode was used to quantify up to 50 target PFASs and screen and semi-quantify up to 2,266 suspect PFASs in each sample. Machine learning classifiers were used to identify PFASs that were diagnostic of each source type. Four C5-C7 perfluoroalkyl acids and one suspect PFAS (trihydrogen-substituted fluoroethernonanoic acid) were diagnostic of AFFF-GW. Two target PFASs (5:3 and 6:2 fluorotelomer carboxylic acids) and two suspect PFASs (4:2 fluorotelomer-thia-acetic acid and N-methylperfluoropropane sulfonamido acetic acid) were diagnostic of landfill leachate. Biosolids leachates were best classified along with landfill leachates and N-methyl and N-ethyl perfluorooctane sulfonamido acetic acid assisted in that classification. WWTP, pulp and paper, and power generation samples contained few target PFASs, but fipronil (a fluorinated insecticide) was diagnostic of WWTP samples. Our results provide PFAS fingerprints for known sources and identify target and suspect PFASs that can be used for source allocation.

Enhanced removal of perfluorooctanoic acid with sequential photocatalysis and fungal treatment

In this paper, we report the degradation of perfluorooctanoic acid (PFOA), which is a persistent contaminant in the environment that can severely impact human health, by exposing it to a photocatalyst, bismuth oxyiodide (BiOI), containing both Bi4O5I2 and Bi5O7I phases and a fungal biocatalyst (Cunninghamella elegans). Individually, the photocatalyst (after 3 h) and biocatalyst (after 48 h) degraded 35–40% of 100 ppm PFOA with 20–30% defluorination. There was a marked improvement in the degree of degradation (90%) and defluorination (60%) when PFOA was first photocatalytically treated, then exposed to the fungus. GC- and LC–MS analysis identified the products formed by the different treatments. Photocatalytic degradation of PFOA yielded short-chain perfluorocarboxylic acids, whereas fungal degradation yielded mainly 5:3 fluorotelomer carboxylic acid, which is a known inhibitor of cytochrome P450-catalysed degradation of PFAS in C. elegans. The combined treatment likely resulted in greater degradation because photocatalysis reduced the PFOA concentration without generating the inhibitory 5:3 fluorotelomer carboxylic acid, enabling the fungus to remove most of the remaining substrate. In addition, new fluorometabolites were identified that shed light on the initial catabolic steps involved in PFOA biodegradation.

Photocatalytical transformation of fluorotelomer- and perfluorosulfonamide-based PFAS on mineral surfaces and soils in aqueous suspensions

Per- and polyfluorinated substances (PFAS) are widely used industrial and household chemicals and occur on various contaminated field sites. To better understand their behavior on soils, spike experiments were performed with 6:2 diPAP (6:2 polyfluoroalkyl phosphate diester) on pure mineral phases (titanium dioxide, goethite and silicon dioxide) in aqueous suspensions under artificial sunlight. Further experiments were performed with uncontaminated soil and four precursor PFAS. Titanium dioxide (referenced as 100 %) showed the highest reactiveness to transform 6:2 diPAP to its primary metabolite 6:2 fluorotelomer carboxylic acid, followed by goethite with the addition of oxalate (4.7 %), silicon dioxide (1.7 %) and soil (0.0024 %). Experiments with four precursors [6:2 diPAP, 6:2 fluorotelomer mercapto alkyl phosphate (FTMAP), N-ethyl perfluorooctane sulfonamide ethanol–based phosphate diester (diSAmPAP), N-ethyl perfluorooctane sulfonamidoacetic acid (EtFOSAA)] on natural soils showed a transformation of all four precursors by simulated sunlight. The production of the primary intermediate from 6:2 FTMAP (6:2 FTSA, rate constant k = 2.7∗10−3h−1) was approximately 13-times faster than from 6:2 diPAP (6:2 FTCA, rate constant k = 1.9∗10−4h−1). EtFOSAA was completely decomposed within 48 h whereas only ~7 % diSAmPAP was transformed in the same time. The primary photochemical transformation product of diSAmPAP and EtFOSAA was PFOA, PFOS was not detected. The production rate constant of PFOA varied significantly between EtFOSAA (k = 0.01h−1) and diSAmPAP (k = 1.3∗10−3h−1). Photochemically produced PFOA consisted of branched and linear isomers and can therefore be used in source tracking. Experiments with different soils suggest that the oxidation of EtFOSAA to PFOA is expected to primarily be driven by hydroxyl radicals, whereas for the oxidation of EtFOSAA to further intermediates, another mechanism instead or in addition to the oxidation by hydroxyl radicals is responsible.

Plasma Protein Binding Evaluations of Per- and Polyfluoroalkyl Substances for Category-Based Toxicokinetic Assessment.

New approach methodologies (NAMs) that make use of in vitro screening and in silico approaches to inform chemical evaluations rely on in vitro toxicokinetic (TK) data to translate in vitro bioactive concentrations to exposure metrics reflective of administered dose. With 1364 per- and polyfluoroalkyl substances (PFAS) identified as of interest under Section 8 of the U.S. Toxic Substances Control Act (TSCA) and concern over the lack of knowledge regarding environmental persistence, human health, and ecological effects, the utility of NAMs to understand potential toxicities and toxicokinetics across these data-poor compounds is being evaluated. To address the TK data deficiency, 71 PFAS selected to span a wide range of functional groups and physico-chemical properties were evaluated for in vitro human plasma protein binding (PPB) by ultracentrifugation with liquid chromatography-mass spectrometry analysis. For the 67 PFAS successfully evaluated by ultracentrifugation, fraction unbound in plasma (fup) ranged from less than 0.0001 (pentadecafluorooctanoyl chloride) to 0.7302 (tetrafluorosuccinic acid), with over half of the PFAS showing PPB exceeding 99.5% (fup < 0.005). Category-based evaluations revealed that perfluoroalkanoyl chlorides and perfluorinated carboxylates (PFCAs) with 6-10 carbons were the highest bound, with similar median values for alkyl, ether, and polyether PFCAs. Interestingly, binding was lower for the PFCAs with a carbon chain length of ≥11. Lower binding also was noted for fluorotelomer carboxylic acids when compared to their carbon-equivalent perfluoroalkyl acids. Comparisons of the fup value derived using two PPB methods, ultracentrifugation or rapid equilibrium dialysis (RED), revealed RED failure for a subset of PFAS of high mass and/or predicted octanol-water partition coefficients exceeding 4 due to failure to achieve equilibrium. Bayesian modeling was used to provide uncertainty bounds around fup point estimates for incorporation into TK modeling. This PFAS PPB evaluation and grouping exercise across 67 structures greatly expand our current knowledge and will aid in PFAS NAM development.

Degradation of 8:2 fluorotelomer carboxylic acid (8:2 FTCA) by plants and their co-existing microorganisms

8:2 fluorotelomer carboxylic acid (8:2 FTCA), an important precursor of perfluorocarboxylic acids (PFCAs), is widely detected in environment and biotas. Hydroponic exposures were conducted to investigate the accumulation and metabolism of 8:2 FTCA in wheat (Triticum aestivum L.) and pumpkin (Cucurbita maxima L.). Endophytic and rhizospheric microorganisms co-existing with the plants were isolated to investigate their contributions to degrade 8:2 FTCA. Wheat and pumpkin roots could take up 8:2 FTCA efficiently with the root concentration factor (RCF) as 5.78 and 8.93, respectively. 8:2 FTCA could be biotransformed to 8:2 fluorotelomer unsaturated carboxylic acid (8:2 FTUCA), 7:3 fluorotelomer carboxylic acid (7:3 FTCA), and seven PFCAs with 2–8 carbon chain length in plant roots and shoots. Cytochromes P450 (CYP450) and glutathione-S-transferase (GST) activities in plants were significantly increased, while flavin-dependent monooxygenases (FMOs) activities were not changed, suggesting that CYP 450 and GST were involved in the transformation of 8:2 FTCA in plant tissues. Twelve 8:2 FTCA-degrading endophytic (8 strains) and rhizospheric (4 strains) bacterial strains were isolated from root interior, shoot interior and rhizosphere of plants, respectively. These bacteria were identified as Klebsiella sp. based on the morphology and 16S rDNA sequence, and they could biodegrade 8:2 FTCA to intermediates and stable PFCAs.

Integration of target, suspect, and nontarget screening with risk modeling for per- and polyfluoroalkyl substances prioritization in surface waters

Though thousands of per- and polyfluoroalkyl substances (PFAS) have been on the global market, most research focused on only a small fraction, potentially resulting in underestimated environmental risks. Here, we used complementary target, suspect, and nontarget screening for quantifying and identifying the target and nontarget PFAS, respectively, and developed a risk model considering their specific properties to prioritize the PFAS in surface waters. Thirty-three PFAS were identified in surface water in the Chaobai river, Beijing. The suspect and nontarget screening by Orbitrap displayed a sensitivity of > 77%, indicating its good performance in identifying the PFAS in samples. We used triple quadrupole (QqQ) under multiple-reaction monitoring for quantifying PFAS with authentic standards due to its potentially high sensitivity. To quantify the nontarget PFAS without authentic standards, we trained a random forest regression model which presented the differences up to only 2.7 times between measured and predicted response factors (RFs). The maximum/minimum RF in each PFAS class was as high as 1.2–10.0 in Orbitrap and 1.7−22.3 in QqQ. A risk-based prioritization approach was developed to rank the identified PFAS, and four PFAS (i.e., perfluorooctanoic acid, hydrogenated perfluorohexanoic acid, bistriflimide, 6:2 fluorotelomer carboxylic acid) were flagged with high priority (risk index > 0.1) for remediation and management. Our study highlighted the importance of a quantification strategy during environmental scrutiny of PFAS, especially for nontarget PFAS without standards.

Fluorotelomer alcohols are efficiently biotransformed by Cunninghamella elegans.

Cunninghamella elegans is a well-studied fungus that biotransforms a range of xenobiotics owing to impressive cytochrome P450 (CYP) activity. In this paper, we report the biotransformation of 6:2 fluorotelomer alcohol (6:2 FTOH) by the fungus, yielding a range of fluorinated products that were detectable by fluorine-19 nuclear magnetic resonance spectroscopy (19F NMR), gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). Upon incubation with the pre-grown cultures, the substrate (100mg/L) was completely consumed within 48h, which is faster biotransformation than other fungi that have hitherto been studied. The main metabolite formed was the 5:3 fluorotelomer carboxylic acid (5:3 FTCA), which accumulated in the culture supernatant. When the cytochrome P450 inhibitor 1-aminobenzotriazole was included in the culture flasks, there was no biotransformation of 6:2 FTOH, indicating that these enzymes are key to the catalysis. Furthermore, when exogenous 5:3 FTCA was added to the fungus, the standard biotransformation of the drug flurbiprofen was inhibited, strongly suggesting that the main fluorotelomer alcohol biotransformation product inhibits CYP activity and accounts for its accumulation.

Henry’s Law constants of 15 per- and polyfluoroalkyl substances determined by static headspace analysis

While it is thought that some per- and polyfluoroalkyl substances (PFAS) may volatilize from aqueous solutions, experimentally measured Henry’s Law constants (kH, synonymous with air : water partition coefficient) are scarce. This leads to a lack of understanding of the partitioning of PFAS and an inability to predict concentrations above contaminated groundwater (e.g., vapor intrusion). We measured kH for 27 PFAS via headspace analysis and manipulations of the gas to liquid phase ratio. Fifteen PFAS produced mass spectrometry signals suitable for kH measurements. At 25 °C the experimentally measured dimensionless kH were: 0.31 – 2.82 for four fluorotelomer alcohols (FTOHs), 0.09 – 0.18 for three fluorotelomer sulfonates (FTSs), 0.30 – 1.01 for three iodinated PFAS, 0.43 – 0.92 for two sulfonamides, 3.86 for 6:2 fluorotelomer olefin, 0.69 for 8:2 fluorotelomer carboxylic acid, and 0.32 for 8:2 fluorotelomer acrylate. Longer fluoroalkyl chain length resulted in increased kH for FTOHs and FTSs, the only two groups in which chain length was studied. Perfluorinated sulfonates and carboxylates were generally not volatile enough to be measured, even at pH as low as 1, although fluorotelomers of both functional groups were measurably volatile. Temperature effects were well described by the van’t Hoff equation. kH was not significantly different in various environmentally relevant matrices demonstrating the broad applicability of the produced constants.

Tools for Understanding and Predicting the Affinity of Per- and Polyfluoroalkyl Substances for Anion-Exchange Sorbents.

Anion-exchange (AE) sorbents are gaining in popularity for the remediation of anionic per- and polyfluoroalkyl substances (PFAS) in water. However, it is unclear how hydrophobic and electrostatic interactions contribute to anionic PFAS retention. The goal of this study was to understand the effects of PFAS chain length and head group on electrostatic interactions between PFAS and an aminopropyl AE phase. Liquid chromatography-mass spectrometry (LC-MS) was used with an aminopropyl AE guard column to find relative retention times. The average electrostatic potential (EPavg) of each PFAS was calculated, which correlated positively with the PFAS chromatographic retention time, demonstrating the value of EPavg as a proxy for predicting electrostatic interactions between PFAS and the aminopropyl AE phase. The order of greatest to lowest PFAS AE affinity for an aminopropyl column based on chromatographic retention times and electrostatic interactions was n:3 fluorotelomer carboxylic acids (n:3 FtAs) > n:2 fluorotelomer carboxylic acids (n:2 FtAs) > perfluoroalkyl carboxylates (PFCAs) > perfluoroalkyl sulfonamides (FASAs) ∼ n:2 fluorotelomer sulfonates (n:2 FtSs) > perfluoroalkyl sulfonates (PFSAs). This study introduces a methodology for qualitatively characterizing electrostatic interactions between PFAS and AE phases and highlights that electrostatic interactions alone cannot explain the affinity of PFAS for AE resins in water treatment/remediation scenarios.

Occurrence and contamination profile of legacy and emerging per- and polyfluoroalkyl substances (PFAS) in Belgian wastewater using target, suspect and non-target screening approaches

With the growing concern regarding the health risks of per- and polyfluoroalkyl substances (PFAS), there is an increasing demand for the identification of emerging PFAS. This study provides a comprehensive investigation of legacy and emerging PFAS in 16 wastewater treatment plants (WWTPs) in Belgium using target, suspect, and non-target screening methods. Perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPeA) were the dominant compounds in most locations, whereas perfluorooctanoic acid (PFOA) was the most predominant PFAS in WWTP Deurne (Antwerp region). Using a suspect screening approach, 14 PFAS were annotated as confidence level (CL) of 4 or higher and 4 PFAS were annotated as CL 2a and 2b, including aqueous film forming foam (AFFF)-derived PFAS. The compound group of n:3 unsaturated fluorotelomer carboxylic acid was found using non-target screening in the wastewater from WWTP Deurne. Population exposure in a catchment area estimated using population-normalized mass loads (PNML) showed the highest value in the catchment area of WWTP Deurne, implying a potentially higher exposure to PFAS in this community.

Behaviors of 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) in wheat seedlings: Bioaccumulation, biotransformation and ecotoxicity

As a new alternative to perfluorooctane sulfonate (PFOS), 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) has been currently used in industrial and consumer applications, which has been frequently detected in environment media. However, the behaviors of 6:2 FTAB in plants are still unclear. This study investigated the bioaccumulation, biotransformation and ecotoxicity of 6:2 FTAB in wheat (Triticum aestivum L.) by hydroponic exposure. 6:2 FTAB was easily taken up by roots with the root concentration factor (RCF) as high as 94.8, but difficult to be acropetally translocated in the shoots with the translocation factor (TF) as low as 0.058. Two intermediates and six terminal perfluorocarboxylic acid (PFCA) metabolites were detected in roots and shoots. The detected metabolites included 6:2 fluorotelomer sulfonic acid (6:2 FTSA), 6:2 fluorotelomer carboxylic acid (6:2 FTCA), perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), perfluorobutyric acid (PFBA), pentafluoropropionic acid (PFPrA) and trifluoroacetic acid (TFA), and 6:2 FTSA was the main metabolite. 6:2 FTAB significantly reduced the biomass of plant and prevented chlorophyll (Chl) accumulation, while caused no significant change in malondialdehyde (MDA) content. Significant reduction in glutathione (GSH) contents, excess production of reactive oxygen species (ROS), and obvious inhibition of superoxide dismutase (SOD), catalase (CAT), peroxidase (POD) and glutathione-s-transferase (GST) activities were observed, suggesting damage of antioxidant defense systems and failure to detoxication of 6:2 FTAB in wheat. These findings provide important knowledge for the fate of 6:2 FTAB in plants.