The first quantitative investigation of compounds generated from PFAS, PFAS-containing aqueous film-forming foams and commercial fluorosurfactants in pyrolytic processes.

Pyrolysis as a thermochemical technology is commonly used in waste management and remediation of organic-contaminated soil. This study, for the first time, investigated fluorinated and non-fluorinated compounds emitted from per- and polyfluoroalkyl substances (PFAS) and relevant products upon pyrolysis (200-890 °C) and their formation mechanisms. Approximately 30 non-fluorinated compounds were detected from PFAS-containing aqueous film-forming foams (AFFFs) and commercial surfactant concentrates (SCs) after heating, including glycols and glycol ethers that were predominant at 200 °C. Oxygen (e.g., 1,4-dioxane) and nitrogen heterocycles and benzene were unexpectedly observed at higher temperatures (300-890 °C), which were likely formed as a consequence of the thermal dehydration, dehydrogenation, and intermolecular cyclization of glycols and glycol ethers. Fluorinated volatiles in six major classes were detected at low and moderate temperatures (200-500 °C), including perfluoroalkenes, perfluoroalkyl aldehydes, fluorotelomer alcohols, and polyfluorinated alkanes/alkenes. Several features of the pyrolyses of PFAS suggest that the underlying decomposition mechanism is radical-mediated. Perfluoroheptene thermally decomposed at 200 °C to shorter-chain homologues following a radical chain-scission mechanism. Most of these volatiles observed at low/moderate temperatures were not detected at 890 °C. Ultra-short-chain fluorinated greenhouse gases (e.g., perfluoromethane) were not found.