Thermal transformations of perfluorooctanoic acid (PFOA): Mechanisms, volatile organofluorine emissions, and implications to thermal regeneration of granular activated carbon

Thermal treatment is effective for the removal of perfluorooctanoic acid (PFOA). However, how temperatures, heating methods, and granular activated carbon (GAC) influence pyrolysis of PFOA, and emission risks are not fully understood. We studied thermal behaviors of PFOA at various conditions and analyzed gaseous products using real-time detection technologies and gas chromatography-mass spectrometry (GC-MS). The thermal decomposition of PFOA is surface-mediated. On the surface of quartz, PFOA decomposed into perfluoro-1-heptene and perfluoro-2-heptene, while on GAC, it tended to decompose into 1 H-perfluoroheptane (C₇HF₁₅). Neutral PFOA started evaporating around 100 ℃ without decomposition in ramp heating. During pyrolysis, when PFOA was pre-adsorbed onto GAC, it was mineralized into SiF₄ and produced more than 45 volatile organic fluorine (VOF) byproducts, including perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs). The VOF products were longer-chain (hydro)fluorocarbons (C4-C7) at low temperatures (< 500 ℃) and became shorter-chain (C1-C4) at higher temperatures (> 600 ℃). PFOA transformations include decarboxylation, VOF desorption, further organofluorine decomposition and mineralization in ramp heating of PFOA-laden GAC. Decarboxylation initiates at 120 ℃, but other processes require higher temperatures (>200 ℃). These results offer valuable information regarding the thermal regeneration of PFAS-laden GAC and further VOF control with the afterburner or thermal oxidizer.