Influence of Carbonate Speciation on Hydrated Electron Treatment Processes.

Advanced reduction processes (ARPs) that generate hydrated electrons (eaq-; e.g., UV-sulfite) have emerged as a promising remediation technology for recalcitrant water contaminants, including per- and polyfluoroalkyl substances (PFASs). The effectiveness of ARPs in different natural water matrices is determined, in large part, by the presence of non-target water constituents that act to quench eaq- or shield incoming UV photons from the applied photosensitizer. This study examined the pH-dependent quenching of eaq- by ubiquitous dissolved carbonate species (H2CO3*, HCO3-, and CO32-) and quantified the relative importance of carbonate species to other abundant quenching agents (e.g., H2O, H+, HSO3-, and O2(aq)) during ARP applications. Analysis of laser flash photolysis kinetic data in relation to pH-dependent carbonate acid-base speciation yields species-specific bimolecular rate constants for eaq- quenching by H2CO3*, HCO3-, and CO32- (kH2CO3* = 2.23 ± 0.42 × 109 M-1 s-1, kHCO3- = 2.18 ± 0.73 × 106 M-1 s-1, and kCO32- = 1.05 ± 0.61 × 105 M-1 s-1), with quenching dominated by H2CO3* (which includes both CO2(aq) and H2CO3) at moderately alkaline pH conditions despite it being the minor species. Attempts to apply previously reported rate constants for eaq- quenching by CO2(aq), measured in acidic solutions equilibrated with CO2(g), overpredict quenching observed in this study at higher pH conditions typical of ARP applications. Moreover, kinetic simulations reveal that pH-dependent trends reported for UV-sulfite ARPs that have often been attributed to eaq- quenching by varying [H+] can instead be ascribed to variable acid-base speciation of dissolved carbonate and the sulfite sensitizer.

Application of High-Resolution Mass Spectrometry to Evaluate UV-Sulfite-Induced Transformations of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF).

UV-sulfite has been shown to effectively degrade per- and polyfluoroalkyl substances (PFASs) in single-solute experiments. We recently reported treatment of 15 PFASs, including perfluoroalkyl sulfonic acids (PFSAs), perfluoroalkyl carboxylic acids (PFCAs), and fluorotelomer sulfonic acids (FTSs), detected in aqueous film-forming foam (AFFF) using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Here, we extend the analysis within those original reaction solutions to include the wider set of PFASs in AFFF for which reactivity is largely unknown by applying recently established LC-QTOF-MS suspect screening and semiquantitative analysis protocols. Sixty-eight additional PFASs were detected (15 targeted + 68 suspect screening = 83 PFASs) with semiquantitative analysis, and their behavior was binned on the basis of (1) detection in untreated AFFF, (2) PFAS photogeneration, and (3) reactivity. These 68 structures account for an additional 20% of the total fluorine content in the AFFF (targeted + suspect screening = 57% of total fluorine content). Structure-reactivity trends were also revealed. During treatment, transformations of highly reactive structures containing sulfonamide (-SO2N-) and reduced sulfur groups (e.g., -S- and -SO-) adjacent to the perfluoroalkyl [F(CF2)n-] or fluorotelomer [F(CF2)n(CH2)2-] chain are likely sources of PFCA, PFSA, and FTS generation previously reported during the early stages of reactions. The results also show the character of headgroup moieties adjacent to the F(CF2)n-/F(CF2)n(CH2)2- chain (e.g., sulfur oxidation state, sulfonamide type, and carboxylic acids) and substitution along the F(CF2)n- chain (e.g., H-, ketone, and ether) together may determine chain length-dependent reactivity trends. The results highlight the importance of monitoring PFASs outside conventional targeted analytical methodologies.

Pilot-scale field demonstration of a hybrid nanofiltration and UV-sulfite treatment train for groundwater contaminated by per- and polyfluoroalkyl substances (PFASs).

Previous laboratory scale studies indicate nanofiltration (NF) and UV-sulfite photochemical treatments as promising technologies for the removal and destruction, respectively, of per- and polyfluoroalkyl substances (PFASs) from contaminated water. This study reports on a field demonstration of a pilot-scale hybrid NF and UV-sulfite treatment train for the remediation of 12 PFASs detected in groundwater impacted by aqueous film-forming foam (AFFF) at a U.S. Department of Defense installation. For most of the detected PFASs, NF rejection was consistently ≥ 95% over a 30-day field trial when operating at 90% total permeate recovery. Rejection of short-chain perfluorosulfonic acids (PFSAs) by NF decreased when recoveries increased from 90 to 97%; tests with a reverse osmosis (RO) membrane showed ≥ 99% rejection of all PFASs regardless of increasing recovery. UV treatment of the NF reject following 90% permeate recovery resulted in variable destruction of individual PFASs, with rates also being dependent on pH and the identity and concentration of UV photosensitizer. Rates of perfluorocarboxylic acid (PFCA) degradation were greater than those measured for PFSAs and perfluoroalkyl acid (PFAA) precursors and were independent of perfluoroalkyl chain length. In contrast, rates of PFSA degradation increased with increasing chain length. Consistent levels of PFAS degradation by UV-sulfite were observed during a 30-day demonstration experiment in NF reject water amended with 10 mM sulfite and adjusted to pH 11.2. Collectively, > 75% of the detected PFAS mass in the NF reject was destroyed after 4 h of UV treatment, increasing to > 90% after 8 h of treatment. An analysis of electrical energy inputs for the hybrid NF/UV-sulfite treatment train showed energy per order magnitude (EE/O) requirements ranging from ≤ 13.1 kWh/m3 for PFCAs and 14.1 kWh/m3 for PFOS to values > 100 kWh/m3 for more recalcitrant short-chain PFSA analogues. The UV reactor and water-cooling system were the major contributors to overall energy requirements and represent the greatest opportunities for improving efficiency of the technology.

Destruction of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment.

Ultraviolet photochemical reaction of sulfite (SO32-) photosensitizer generates strongly reducing hydrated electrons (eaq-; NHE = -2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize eaq- reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via eaq- reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.