Removal of per- and polyfluoroalkyl substances from water by plasma treatment: Insights into structural effects and underlying mechanisms

Non-thermal plasma emerges as a promising technology for per- and polyfluoroalkyl substances (PFAS) decomposition due to its notable efficacy and environmentally friendly characteristics. In this study, we demonstrated the efficacy of a falling film dielectric barrier discharge (DBD) system for the removal of 10 PFAS, including perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs) and hexafluoropropylene oxide (HFPO) oligomer acids. Results showed that compounds with fluoroalkyl chain length>4 were effectively decomposed within 100 min, with long-chain PFAS demonstrating more pronounced removal performance than their short-chain analogues. The superior removal but low defluorination observed in HFPO oligomer acids could be ascribed to their ether-based structural features. The integration of experimental results with density functional theory (DFT) calculations revealed that the synergistic effects of various reactive species are pivotal to their efficient decomposition, with electrons, OH center dot, and NO2 center dot playing essential roles. In contrast, the degradation of PFSAs was more dependent on electron attack than that of PFCAs and HFPO oligomer acids. Significantly, the most crucial degradation pathway for HFPO oligomer acids was the cleavage of ether CO, whether through radical or electron attack. Furthermore, the demonstrated effective removal in various water matrices showed the potential of the plasma system for removing PFAS in complex aquatic environments. This study provided mechanistic insights into PFAS degradation behavior in plasma processes, and it underscored the vital influence of molecular structures on degradability, thereby contributing to the further development and regulation of plasma-based technologies for treating PFAS in water.