Incinerability of PFOA and HFPO-DA: Mechanisms, kinetics, and thermal stability ranking

Abstract

Thermal treatment is currently the only full-scale technology for the destruction of per- and polyfluoroalkyl substances (PFAS) in wastes. However, concerns exist about the emission of incomplete combustion products from incinerators. To address critical knowledge gaps around the incinerability of PFAS, highest-level coupled cluster theory was applied to elucidate the primary thermal destruction pathways, mechanisms, and kinetics for perfluorooctanoic acid (PFOA) and hexafluoropropylene oxide dimer acid (HFPO-DA, sometimes referred to as “GenX”). These PFAS were then ranked based on U.S. EPA's Thermal Stability Index, which ranges from Class 1 for the most thermally stable chemicals to Class 7 for the most thermally labile chemicals. Initial decomposition of both carboxylic acids proceeds through HF elimination at the α-carbon, but for PFOA surprisingly shifts towards C-COOH bond dissociation in the presence of ammonia due to ammonium stabilization of the variational transition state. Branching substantially reduces the required incineration temperatures, while chain length has no impact on perfluoroalkyl carboxylic acid (PFCA) decomposition rates. Bimolecular reactions with secondary species such as counterions and radicals have lower activation barriers than unimolecular decomposition, but their second-order kinetics depend on concentration and thus waste stream composition, which varies in practice. Simulating radical concentrations under typical incineration conditions, the determined free energies of activation suggest an incinerability ranking for linear PFOA in Class 3, for branched PFOA in Class 4, and for HFPO-DA as well as both PFOA and HFPO-DA ammonium salts in Class 5. Collectively, the temperatures needed to destroy 99.99% of PFOA, HFPO-DA, and other PFCAs in 2 seconds gas residence time are well below those of other commonly incinerated organic compounds such as chlorobenzene (Class 1). Ultimately, sufficient supply of radical donors is critical to ensure safe, efficient, and complete destruction of PFAS during thermal treatment.