Effect of Dissolved Organic Matter on the Photodegradation of Decachlorobiphenyl (PCB-209) in Heterogeneous Systems: Experimental Analysis and Excited-State Theory Calculations

Dissolved organic matter (DOM) can affect the transformation of pollutants through photosensitization, but most current research focuses on hydrophilic pollutants, making it such that less attention is paid to hydrophobic pollutants. In this paper, the effect and action mechanism of coexisting DOM on the photodegradation of decachlorobiphenyl (PCB-209) on suspended particles collected from the Yellow River were systematically investigated in a heterogeneous system using DOM standards and model compounds. Through molecular probe experiments, mass spectrometry analysis and theoretical calculations, we found that the excited triplet state of DOM (3DOM*) could excite PCB-209 to undergo dechlorination reaction. Due to the different modes of electron transition, the presence of carbonyl groups decreased the energy of 3DOM*, whereas the electron-donating groups made the energy of 3DOM* higher. DOM containing phenolic hydroxyl groups led to a higher steady-state concentration of •OH, and DOM containing phenyl ketone structures had a stronger ability to produce •O2–. Compared with aqueous •OH, •O2– produced from hydrophobic microregions could react more readily with PCB-209. This study deepens the understanding of the role of different functional groups of DOM in the photosensitized transformation of hydrophobic compounds.