Photoformation of environmentally persistent free radicals on particulate organic matter in aqueous solution: Role of anthracene and formation mechanism

Environmentally persistent free radicals (EPFRs) generated under irradiation have been widely detected in soil particles, atmospheric particles and microplastic particles, but the formation of EPFRs in water is not well understood. This study investigated the formation of EPFRs on particulate organic matter (POM) in water contaminated by anthracene (Ant) under irradiation. The photoformation and decay progress of EPFRs was represented with the help of electron paramagnetic resonance (EPR) technique on both actual POM and Fe(III)-montmorillonite simulated samples. EPR signals at the range of 1016 to 1017 spin/g were detected and the half-life time of EPFRs stored in water was at around 16.62 h and 60.80 h, much shorter than those in the air. The g factors were all larger than 2.0040, which indicated the generation of oxygen centered EPFRs. The primary intermediates were identified by gas chromatography-mass spectrometer (GC-MS) and a possible EPFR formation pathway during Ant degradation was proposed. The interaction between Ant and POM, and the hydroxylation and carbonylation of the intermediates made contributions to the generation of EPFRs. Meanwhile, the indirect photodegradation of bisphenol A (BPA) has been demonstrated by analyzing the reactive oxygen species (ROS) and photogenerated electrons in the solution with POM containing EPFRs. It is found that hydroxyl radicals (•OH) and singlet oxygen (1O2) were induced and might promote the photodegration. Overall, our present study provided useful information to understand the photoformation of EPFRs on POM and their fate in aqueous environments.