Defluorination of Per- and Polyfluoroalkyl Substances (PFASs) with Hydrated Electrons: Structural Dependence and Implications to PFAS Remediation and Management

, leads to the elucidation of new mechanistic insights into PFAS degradation. Theoretical calculations on the C-F bond dissociation energies (BDEs) of all PFAS structures reveal strong relationships among (i) the rate and extent of decay and defluorination, (ii) head functional groups, (iii) fluoroalkyl chain length, and (iv) the position and number of C-F bonds with low BDEs. These relationships are further supported by the spontaneous cleavage of specific bonds during calculated geometry optimization of PFAS structures bearing one extra electron, and by the product analyses with high-resolution mass spectrometry. Multiple reaction pathways, including H/F exchange, dissociation of terminal functional groups,…

• NS
  National Science Foundation
• UO
  University of California, Riverside
• SE
  Strategic Environmental Research and Development Program

  Awards: ER-1497, ER-1289
• DO
  Division of Chemistry

  Awards: CHE-1709719, CHE-1709286