New Insights into Thermal Degradation Products of Long-Chain Per- and Polyfluoroalkyl Substances (PFAS) and Their Mineralization Enhancement Using Additives

The products of incomplete destruction (PIDs) of per- and polyfluoroalkyl substances (PFAS) represent a substantial ambiguity when employing thermal treatments to remediate PFAS-contaminated materials. In this study, we present new information on PIDs produced in both inert and oxidative environments from five long-chain PFAS, including three now regulated under the U.S. Safe Drinking Water Act, one cationic precursor compound, and one C10 PFAS. The data did not support the generation of tetrafluoromethane from any of the studied PFAS, and carbonyl fluoride was found only from potassium perfluorooctanesulfonate (K-PFOS) when heated in air in a narrow temperature range. Oxidative conditions (air) were observed to facilitate PFAS thermal degradation and accelerate the mineralization of K-PFOS. Spectroscopic data suggest that PFAS thermal degradation is initiated by the cleavage of bonds that form perfluoroalkyl radicals, leading to organofluorine PIDs (e.g., perfluoroalkenes). In air, perfluoroalkyl radicals react with oxygen to form oxygen-containing PIDs. The mineralization of PFAS was enhanced by adding solid additives, which were categorized as highly effective (e.g., granular activated carbon (GAC) and certain noble metals), moderately effective, and noneffective. Remarkably, simply by adding GAC, we achieved >90% mineralization of perfluorooctanoic acid at 300 °C and ∼1.9 atm within just 60 min without using water or solvents.