Thermal Stability and Decomposition of Perfluoroalkyl Substances on Spent Granular Activated Carbon

The aims of this study were two-fold: (1) to improve our understanding of the thermal stability of per- and polyfluoroalkyl substances and (2) to investigate their decomposition mechanisms on spent granular activated carbon (GAC) during thermal reactivation. We studied seven perfluoroalkyl carboxylic acids (PFCAs), three perfluoroalkyl sulfonic acids (PFSAs), and one perfluoroalkyl ether carboxylic acid (PFECA) in different atmospheres (N2, O2, CO2, and air). The destabilization of studied compounds during thermal treatment followed first-order kinetics. The temperature needed for thermally destabilizing PFCAs increased with the number of perfluorinated carbons (n CF2). Decomposition of PFCAs such as perfluorooctanoic acid (PFOA) on GAC initiated at temperatures as low as 200 °C. The PFECA was even more readily decomposed than PFCA with the same n CF2. PFSAs such as perfluorooctanesulfonic acid (PFOS), on the other hand, required a much higher temperature (≥450 °C) to decompose. Volatile organofluorine species were the main thermal decomposition product of PFOA and PFOS at low to moderate temperatures (≤600 °C). Efficient mineralization to fluoride ions (>80%) of PFOA and PFOS on GAC occurred at 700 °C or higher, accompanied by near complete PFOA and PFOS decomposition (>99.9%). Thermal decomposition pathways of PFOA were proposed.