Theoretical and experimental insights into the degradation mechanism of PFBS under subcritical hydrothermal conditions

Per- and polyfluoroalkyl substances (PFAS) are known for their strong C-F bonds, which make them highly persistent in the environment and resistant to degradation. Among PFAS, perfluorobutane sulfonate (PFBS), a short-chain PFSA widely used as a replacement for long-chain PFAS like perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), has garnered attention due to its environmental persistence and toxicity. Although PFBS has lower bioaccumulation potential than its long-chain counterparts, it remains a significant pollutant with limited data available on its degradation mechanisms. To address this, the present study investigates PFBS degradation under subcritical water hydrothermal conditions. Various alkaline substances and additives were tested, and degradation products were analyzed by liquid and gas chromatography-mass spectrometry. Results show that 2 M NaOH at 325°C achieved an ∼99.4 % PFBS removal rate, and the degradation pathway began with the breakdown of the S-C bond, followed by C-F bond cleavage, resulting in the formation of smaller fluorinated compounds, including trifluoroacetic acid. Density functional theory (DFT) calculations provided detailed insights into the degradation mechanism, identifying hydroxide ion attack on the sulfonic acid group as the initial step and elucidating three distinct pathways for subsequent reactions. This study provides key insights into PFBS degradation mechanisms, emphasizing the synergistic effect of alkaline bases and additives. The findings support the optimization of subcritical hydrothermal treatment for PFAS removal, providing a scalable and environmentally sustainable solution.