Promotive Effects of Chloride and Sulfate on the Near-Complete Destruction of Perfluorocarboxylates (PFCAs) in Brine via Hydrogen-tuned 185-nm UV Photolysis: Mechanisms and Kinetics.

Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H2) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H2 photolysis on the hydrated electron (eaq-) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of eaq- ([eaq-]ss). Results showed that VUV/H2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant (kdeF) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of eaq- via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to eaq- by H2, which was supported by a linear correlation between the predicted [eaq-]ss and experimentally observed kdeF. The kdeF value increased from pH 9 to 12, which was attributed to the speciation of the H·/eaq- pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.

Oxidative Transformation of Nafion-Related Fluorinated Ether Sulfonates: Comparison with Legacy PFAS Structures and Opportunities of Acidic Persulfate Digestion for PFAS Precursor Analysis.

The total oxidizable precursor (TOP) assay has been extensively used for detecting PFAS pollutants that do not have analytical standards. It uses hydroxyl radicals (HO•) from the heat activation of persulfate under alkaline pH to convert H-containing precursors to perfluoroalkyl carboxylates (PFCAs) for target analysis. However, the current TOP assay oxidation method does not apply to emerging PFAS because (i) many structures do not contain C-H bonds for HO• attack and (ii) the transformation products are not necessarily PFCAs. In this study, we explored the use of classic acidic persulfate digestion, which generates sulfate radicals (SO4-•), to extend the capability of the TOP assay. We examined the oxidation of Nafion-related ether sulfonates that contain C-H or -COO-, characterized the oxidation products, and quantified the F atom balance. The SO4-• oxidation greatly expanded the scope of oxidizable precursors. The transformation was initiated by decarboxylation, followed by various spontaneous steps, such as HF elimination and ester hydrolysis. We further compared the oxidation of legacy fluorotelomers using SO4-• versus HO•. The results suggest novel product distribution patterns, depending on the functional group and oxidant dose. The general trends and strategies were also validated by analyzing a mixture of 100000- or 10000-fold diluted aqueous film-forming foam (containing various fluorotelomer surfactants and organics) and a spiked Nafion precursor. Therefore, (1) the combined use of SO4-• and HO• oxidation, (2) the expanded list of standard chemicals, and (3) further elucidation of SO4-• oxidation mechanisms will provide more critical information to probe emerging PFAS pollutants.

Aerobic Biotransformation and Defluorination of Fluoroalkylether Substances (ether PFAS): Substrate Specificity, Pathways, and Applications.

Fluoroalkylether substances (ether PFAS) constitute a large group of emerging PFAS with uncertain environmental fate. Among them, GenX is the well-known alternative to perfluorooctanoic acid and one of the six proposed PFAS to be regulated by the U.S. Environmental Protection Agency. This study investigated the structure-biodegradability relationship for 12 different ether PFAS with a carboxylic acid headgroup in activated sludge communities. Only polyfluorinated ethers with at least one -CH2- moiety adjacent to or a C=C bond in the proximity of the ether bond underwent active biotransformation via oxidative and hydrolytic O-dealkylation. The bioreactions at ether bonds led to the formation of unstable fluoroalcohol intermediates subject to spontaneous defluorination. We further demonstrated that this aerobic biotransformation/defluorination could complement the advanced reduction process in a treatment train system to achieve more cost-effective treatment for GenX and other recalcitrant perfluorinated ether PFAS. These findings provide essential insights into the environmental fate of ether PFAS, the design of biodegradable alternative PFAS, and the development of cost-effective ether PFAS treatment strategies.

Substantial defluorination of polychlorofluorocarboxylic acids triggered by anaerobic microbial hydrolytic dechlorination.

Chlorinated polyfluorocarboxylic acids (Cl-PFCAs) derived from the widely used chlorotrifluoroethylene (CTFE) polymers and oligomers may enter and influence the aquatic environment. Here, we report significant defluorination of Cl-PFCAs by an anaerobic microbial community via novel pathways triggered by anaerobic microbial dechlorination. Cl-PFCAs first underwent microbial reductive, hydrolytic, and eliminative dechlorination, and it was the hydrolytic dechlorination that led to significant spontaneous defluorination. Hydrolytic dechlorination was favored with increased Cl-substitutions. An isolated, highly enriched anaerobic defluorinating culture was dominated by two genomes closest to Desulfovibrio aminophilus and Sporomusa sphaeroides, both of which exhibited active defluorination of CTFE tetramer acid. It implies the critical role played by anaerobic non-respiratory hydrolytic dechlorination in the fate of chlorinated polyfluoro-chemicals in natural and engineered water environments. The greatly enhanced biodegradability by Cl-substitutions also sheds light on the design of cost-effective treatment biotechnologies, as well as alternative PFAS that are readily biodegradable and less toxic.

Electron-bifurcation and fluoride efflux systems in Acetobacterium spp. drive defluorination of perfluorinated unsaturated carboxylic acids.

Enzymatic cleavage of C-F bonds in per- and polyfluoroalkyl substances (PFAS) is largely unknown but avidly sought to promote systems biology for PFAS bioremediation. Here, we report the reductive defluorination of α, ß-unsaturated per- and polyfluorocarboxylic acids by Acetobacterium spp. Two critical molecular features in Acetobacterium species enabling reductive defluorination are (i) a functional fluoride efflux transporter (CrcB) and (ii) an electron-bifurcating caffeate reduction pathway (CarABCDE). The fluoride transporter was required for detoxification of released fluoride. Car enzymes were implicated in defluorination by the following evidence: (i) only Acetobacterium spp. with car genes catalyzed defluorination; (ii) caffeate and PFAS competed in vivo ; (iii) models from the X-ray structure of the electron-bifurcating reductase (CarC) positioned the PFAS substrate optimally for reductive defluorination; (iv) products identified by 19 F-NMR and high-resolution mass spectrometry were consistent with the model. Defluorination biomarkers identified here were found in wastewater treatment plant metagenomes on six continents.

Microbial Defluorination of Unsaturated Per- and Polyfluorinated Carboxylic Acids under Anaerobic and Aerobic Conditions: A Structure Specificity Study.

The recently discovered microbial reductive defluorination of two C6 branched and unsaturated fluorinated carboxylic acids (FCAs) provided valuable insights into the environmental fate of per- and polyfluoroalkyl substances (PFASs) and potential bioremediation strategies. However, a systematic investigation is needed to further demonstrate the role of C═C double bonds in the biodegradability of unsaturated PFASs. Here, we examined the structure-biodegradability relationships of 13 FCAs, including nine commercially available unsaturated FCAs and four structurally similar saturated ones, in an anaerobic defluorinating enrichment and an activated sludge community. The anaerobic and aerobic transformation/defluorination pathways were elucidated. The results showed that under anaerobic conditions, the α,ß-unsaturation is crucial for FCA biotransformation via reductive defluorination and/or hydrogenation pathways. With sp2 C-F bonds being substituted by C-H bonds, the reductive defluorination became less favorable than hydrogenation. Moreover, for the first time, we reported enhanced degradability and defluorination capability of specific unsaturated FCA structures with trifluoromethyl (-CF3) branches at the α/ß-carbon. Such FCA structures can undergo anaerobic abiotic defluorination in the presence of reducing agents and significant aerobic microbial defluorination. Given the diverse applications and emerging concerns of fluorochemicals, this work not only advances the fundamental understanding of the fate of unsaturated PFASs in natural and engineered environments but also may provide insights into the design of readily degradable fluorinated alternatives to existing PFAS compounds.

Structure-Specific Aerobic Defluorination of Short-Chain Fluorinated Carboxylic Acids by Activated Sludge Communities.

Per- and polyfluoroalkyl substances (PFAS) are a large group of manmade chemicals that impose emerging environmental concerns. Among them, short-chain per- and polyfluorinated carboxylic acids represent an important subgroup used as building blocks of biologically active chemicals and functional materials. Some are also considered PFAS alternatives, and some could be byproducts of the physicochemical treatment of PFAS. However, little is known about the environmental fate of short-chain fluorinated carboxylic acids (FCAs) and their defluorination/transformation by microorganisms. To fill the knowledge gap, we investigated the structure-reactivity relationships in the aerobic defluorination of C3-C5 FCAs by activated sludge communities. Four structures exhibited greater than 20% defluorination, with 3,3,3-trifluoropropionic acid being almost completely defluorinated. We further analyzed the defluorination/transformation pathways and inferred the structures susceptible to aerobic microbial defluorination. We also demonstrated that the defluorination was via cometabolism. The findings advance the fundamental understanding of aerobic microbial defluorination and help assess the environmental fate of PFAS. Since some short-chain PFAS, such as 3,3,3-trifluoropropionic acid, are the incomplete defluorination byproducts of advanced reduction processes, their defluorination by activated sludge communities sheds light on the development of cost-effective chemical-biological PFAS treatment train systems.

In Vivo Generation of PFOA, PFOS, and Other Compounds from Cationic and Zwitterionic Per- and Polyfluoroalkyl Substances in a Terrestrial Invertebrate (Lumbricus terrestris).

Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) are two environmentally persistent per- and polyfluoroalkyl substances (PFAS) that have been detected globally in human tissues and fluids. As part of a project investigating the indirect sources of PFOA/PFOS in the environment and engineered systems, this study is concerned with the mechanisms leading to their in vivo generation in terrestrial invertebrates. We demonstrate here the formation of PFOA and PFOS in earthworms (Lumbricus terrestris) from a group of four zwitterionic/cationic polyfluoroalkyl amides and sulfonamides. In bioaccumulation tests, the zwitterionic PFAS compounds were metabolized within 10 days to PFOA/PFOS at yields of 3.4-20.8 mol % by day 21 and several infrequently reported PFAS species for which chemical structures were determined using high-resolution mass spectrometry. Cationic PFAS, on the other hand, were found to be much less metabolizable in terms of the number (n = 2) and yields (0.9-5.1 mol %) of metabolites. Peak-shaped bioaccumulation profiles were frequently observed for the studied PFAS. Residual zwitterionic/cationic PFAS in earthworms were detected at the end of the elimination phase, indicating that not all zwitterionic/cationic PFAS molecules in vivo are available for enzymatic degradation. Finally, the relative importance of different exposure routes (i.e., waterborne and dietary exposure) was investigated.

Sorption and Desorption Mechanisms of Cationic and Zwitterionic Per- and Polyfluoroalkyl Substances in Natural Soils: Thermodynamics and Hysteresis.

Sorption linearity and reversibility are implicit in models for the fate and transport of per- and polyfluoroalkyl substances (PFAS). In this study, however, we found that the sorption of cationic and zwitterionic PFAS in natural soils was highly nonlinear. The nonlinearity was so severe that it led to a variation in the coefficient of sorption by several orders of magnitude over the experimental concentration range. This implies a considerable increase in sorption as concentration falls in the natural environment. Sorption of cationic PFAS correlated strongly with the soil organic matter (SOM) content and was reversible in all soils. Sorption of zwitterionic PFAS, on the other hand, displayed concentration-dependent hysteresis in soils with a low SOM content. The irreversibility, which was associated with neither SOM, pore deformation, nor surface complexation, was likely caused by the entrapment of molecules in porous structures within inorganic components of soil aggregates. Furthermore, electrostatic interactions with negatively charged soil constituents and the hydrophobic effect were found to be major sorption driving forces for cationic/zwitterionic PFAS at low and high concentrations, respectively. The maximum electrostatic potential of PFAS ions, computed using density functional theory, was found to be a useful predictor of the sorption of ionic PFAS species.