Transformation of dissolved organic matter during UV/peracetic acid treatment

Peracetic acid combined ultraviolet (UV/PAA) process has garnered growing attention as a promising advanced oxidation process (AOP) for wastewater treatment, but the corresponding transformation of ubiquitous dissolved organic matter (DOM) under this AOP remains unknown. This study systematically investigated the changes in characteristics and composition of DOM under UV/PAA, as well as the underlying mechanisms by multiple spectroscopic analyses and Fourier transform ion cyclotron resonance mass spectrometry. UV/PAA treatment dramatically decreased aromaticity, apparent molecular weight, and fluorescent abundance of DOM with the production of more oxidized and saturated compounds. The reactive species (i.e., ^·OH and CH₃C(O)O^·/CH₃C(O)OO^·) in UV/PAA contributed primarily to DOM changes but showed different reaction selectivity and mechanisms. ^·OH reacts with DOM components and mainly yields oxygenation products via a radical addition pathway. Comparatively, the electron transfer route is more likely to occur in CH₃C(O)O^·/CH₃C(O)OO^·-induced DOM transformation. Aside from oxygenation products, electron transfer could exclusively generate decarboxylation products and distinguishes CH₃C(O)O^·/CH₃C(O)OO^·-based AOPs from ^·OH-based AOPs. These findings significantly improve knowledge of DOM alterations under UV/PAA AOP at both the bulk and molecular levels.