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Granular activated carbon (GAC) is widely used to treat contaminated per- and polyfluoroalkyl substances (PFAS) waste streams, resulting in the accumulation of large quantities of spent GAC that need to be landfilled or regenerated. A novel modified supercritical CO 2 (scCO 2 ) extraction for regeneration of spent GAC is developed. With the addition of organic solvents and acid modifiers, the procedure yielded >99% perfluorooctanoic acid (PFOA) desorption after a 60-min treatment in a continuous flow reactor. The mild extraction conditions at T ∼100 °C do not trigger the formation of volatile organic fluorine or changes in GAC sorbent properties. Mechanistically, the high miscibility of co-solvent/scCO 2 eliminates diffusion transport limitations, enabling rapid reagent and PFAS transport in a single-phase (gas-like) medium. The introduction of organic co-solvent and the absence of water reverses hydrophobic interactions between GAC and the PFAS. The acid modifier minimizes the electrostatic PFOA/GAC interactions by protonating the perfluorooctanoate ion and providing competition for active GAC sites. The approach offers an economically effective regeneration scheme, enabling the reuse of sorbents and yielding effluent with a high loading of PFAS that is amenable to subsequent end-of-life treatment technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) have received increased attention due to their environmental prevalence and threat to public health. Trifluoroacetic acid (TFA) is an ultrashort-chain PFAS and the simplest perfluorocarboxylic acid (PFCA). While the US EPA does not currently regulate TFA, its chemical similarity to other PFCAs and its simple molecular structure make it a suitable model compound for studying the transformation of PFAS. We show that hydrothermal processing in compressed liquid water transforms TFA at relatively mild conditions (T = 150-250 °C, P < 30 MPa), initially yielding gaseous products, such as CHF 3 and CO 2 , that naturally aspirate from the solution. Alkali amendment ( e.g ., NaOH) promotes the mineralization of CHF 3 , yielding dissolved fluoride, formate, and carbonate species as final products. Fluorine and carbon balances are closed using Raman spectroscopy and fluoride ion selective electrode measurements for experiments performed at alkaline conditions, where gas yields are negligible. Qualitative FTIR gas analysis allows for establishing the transformation pathways; however, the F-balance could not be quantitatively closed for experiments without NaOH amendment. The kinetics of TFA transformation under hydrothermal conditions are measured, showing little to no dependency on NaOH concentration, indicating that the thermal decarboxylation is a rate-limiting step. A proposed TFA transformation mechanism motivates additional work to generalize the hydrothermal reaction pathways to other PFCAs.

As regulations are being established to limit the levels of per- and polyfluoroalkyl substances (PFAS) in drinking water and wastewater, effective treatment technologies are needed to remove or destroy PFAS in contaminated liquid matrices. Many military installations and airports have fire training ponds (FTPs) where PFAS-containing firefighting foams are discharged during training drills. FTP water disposal is expensive and challenging due to the high PFAS levels. Hydrothermal alkaline treatment (HALT) has previously been shown to destroy a wide range of PFAS compounds with a high degree of destruction and defluorination. In this study, we investigate the performance of a continuous flow HALT reactor for destroying PFAS in contaminated FTP water samples. Processing with 5 M-NaOH and 1.6 min of continuous processing results in >99% total PFAS destruction, and 10 min processing time yields >99% destruction of every measured PFAS species. Operating with 0.1 M-NaOH or 1 M-NaOH shows little effect on the destruction of measured perfluorosulfonic acids, while all measured perfluorocarboxylic acids and fluorotelomer sulfonates are reduced to levels below the method detection limits. Continuous HALT processing with sufficient NaOH loading appears to destroy parent PFAS compounds significantly faster than batch HALT processing, a positive indicator for scaling up HALT technology for practical applications in environmental site remediation activities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)