Theoretical and experimental insights into the mechanisms of C6/C6 PFPiA degradation by dielectric barrier discharge plasma

Abstract

As an emerging alternative legacy perfluoroalkyl substance, C6/C6 PFPiA (perfluoroalkyl phosphinic acids) has been detected in aquatic environments and causes potential risks to human health. The degradation mechanisms of C6/C6 PFPiA in a dielectric barrier discharge (DBD) plasma system were explored using validated experimental data and density functional theory (DFT) calculations. Approximately 94.5% of C6/C6 PFPiA was degraded by plasma treatment within 15 min at 18 kV. A relatively higher discharge voltage and alkaline conditions favored its degradation. C6/C6 PFPiA degradation was attributed to attacks of •OH, •O₂^-, and ¹O₂. Besides PFHxPA and C2 -C6 shorter-chain perfluorocarboxylic acids, several other major intermediates including C4/C6 PFPiA, C4/C4 PFPiA, and C3/C3 PFPiA were identified. According to DFT calculations, the potential energy surface was proposed for possible reactions during C6/C6 PFPiA degradation in the discharge plasma system. Integrating the identified intermediates and DFT results, C6/C6 PFPiA degradation was deduced to occur by stepwise losing CF₂, free radical polymerization, and C-C bond cleavage. Furthermore, the DBD plasma treatment process decreased the toxicity of C6/C6 PFPiA to some extent. This study provides a comprehensive understanding of C6/C6 PFPiA degradation by plasma advanced oxidation.

Keywords: DFT calculation; Degradation mechanisms; Discharge plasma; Perfluoroalkyl phosphinic acids.