Byproducts produced when treating perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water using a plasma treatment process intentionally operated to treat these compounds slowly to allow for byproduct accumulation were quantified. Several linear chain perfluoroalkyl carboxylic acids (PFCAs) (C4 to C7) were identified as byproducts of both PFOA and PFOS treatment. PFOA, perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS) were also found to be byproducts from PFOS degradation. Significant concentrations of fluoride ions, inorganic carbon, and smaller organic acids (trifluoroacetic acid, acetic acid, and formic acid) were also identified. In addition to PFCAs, PFHxS, and PFBS, trace amounts of 43 PFOA-related and 35 PFOS-related byproducts were also identified using a screening and search-based algorithm. Minor concentrations of gas-phase byproducts were also identified (<2.5% of the F originally associated with the parent molecules) some of which are reported for the first time in perfluoroalkyl substance degradation experiments including cyclic perfluoroalkanes (C4F8, C5F10, C6F12, C7F14, and C8F16). The short chain PFCAs detected suggest the occurrence of a stepwise reduction of the parent perfluoroalkyl substances (PFAS) molecule, followed by oxidation of intermediates, perfluoroalkyl radicals, and perfluoro alcohols/ketones. Using a fluorine mass balance, 77% of the fluorine associated with the parent PFOA and 58% of the fluorine associated with the parent PFOS were identified. The bulk of the remaining fluorine was determined to be sorbed to reactor walls and tubing using sorption experiments in which plasma was not generated.

A pilot-scale plasma reactor installed into an 8 × 20 ft 2 mobile trailer was used to rapidly and effectively degrade poly-and perfluoroalkyl substances (PFAS) from liquid investigation-derived waste (IDW; development and purge water from monitoring wells) obtained from 13 different site investigations at Air Force installations. In the raw water, numerous PFAS were detected in a wide concentration range (∼10−10 5 ng/L; total oxidizable precursors (TOP) ∼10 2 −10 5 ng/L, total fluorine by combustion ion chromatography ∼10 2 to 5 × 10 6 ng F/L). The concentration of total PFAS (12 perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFSAs)) in the 13 samples ranged between 2.7 and 1440 μg/L and the concentration of perfluorooctane sulfonate (PFOS) plus perfluorooctanoic acid (PFOA) ranged between 365 and 73700 ng/L. Plasma-based water treatment resulted in rapid perfluoroalkyl acids (PFAAs) removal from 4 L individual IDW samples with faster rates for longer-chain PFCAs (C ≥ 8) and PFSAs (C ≥ 6) than for PFCAs and PFSAs of shorter chain length. In 9 of the 13 IDW samples, both PFOS and PFOA were removed to below United States Environmental Protection Agency's (USEPA's) health advisory concentration level (HAL) concentrations in <1 min, whereas longer treatment times (up to 50 min) were required for the remaining four IDW samples due to either extremely high solution electrical conductivity, which decreased the plasma−liquid contact area (one IDW sample) or high concentrations of PFAAs and their precursors; the latter was found to be converted to PFAAs during the treatment. Overall, 36−99% of the TOP concentration present in the IDWs was removed during the treatment. There was no effect of non-PFAS co-contaminants on the degradation efficiency. Overall, the results indicate that plasma-based water treatment is a viable technology for the treatment of PFAS-contaminated IDW.

“High-concentration” and “low-concentration” bench-scale batch plasma reactors were used to effectively degrade per- and polyfluoroalkyl substances (PFAS) at a high concentration (∼100 mg/L) and a low concentration (<1 μg/L), respectively, in ion exchange (IX) regenerant still bottom (SB) solutions. In the SBs, numerous PFAS were detected with a wide concentration range (∼0.01 to 100 mg/L; total oxidizable precursors (TOP) ∼4000 to 10000 mg/L). In the “high-concentration” plasma reactor, the concentrations of PFAS precursors and long-chain perfluoroalkyl acids (PFAAs) (≥6C for PFSAs and ≥8C for perfluorocarboxylic acids (PFCAs)) were decreased by >99.9% in 2 h, and short-chain PFAAs (<6C for perfluorocarboxylic acids (PFSAs) and <8C PFCAs) were decreased by >99% in 6 h of treatment. Subsequently, a “low concentration” plasma reactor was used to remove additional PFAAs. In this reactor, the addition of CTAB (cetrimonium bromide, a cationic surfactant) caused short-chain PFAAs, other than PFBA, to be removed to below detection limits in 90 min of treatment time. Overall, >99% of the TOP present in SBs was removed during the treatment. Fluorine recovery of 47 to 117% was obtained in six SB samples. Energy requirement (EE/O) for the treatment of PFOA and PFOS from SBs ranged from 380 to 830 kWh/m3.

A pilot-scale plasma-based water treatment system containing two enhanced contact plasma reactors was deployed to a fire training area at Wright-Patterson Air Force Base to treat poly- and perfluoroalkyl substances (PFAS) in aqueous film-forming foam-impacted groundwater from two monitoring wells, wells B and C. Extracted water from both wells was treated through the plasma trailer in a semibatch mode at flow rates ranging from 2.4 to 8.4 L/min. Long-chain perfluoroalkyl acids (PFAAs; fluorocarbon chain of ≥6) and PFAS precursors were reduced by ≥90% for all flow rates in a single cycle through the reactors. Combined perfluorooctanoic acid and perfluorooctanesulfonic acid concentrations lower than the U.S. Environmental Protection Agency’s health advisory level of 70 ng/L were achieved in fewer than three cycles through the reactors. Short-chain PFAAs (fluorocarbon chain of ≤5) were removed to a lesser extent (0–95%) due to their generation during plasma treatment of long-chain PFAAs and PFAS precursors and limited accumulation at the plasma–liquid interface of the reactor. To improve the destruction of short-chain PFAAs, batch mode experiments were performed with the addition of a cationic surfactant (cetrimonium bromide), resulting in an 88% reduction of all short-chain PFAAs within 120 min of treatment.

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