Formation of free radicals by direct photolysis of halogenated phenols (HPs) and effects of DOM: A case study on monobromophenols.

The free radicals play an important role to understand direct/indirect transformation mechanisms of organic pollutants. However, very few efforts have been made to elucidate the radicals produced by direct photolysis. In this study, the short-lived radicals generated under simulated sunlight irradiation from representative halogenated phenols (HPs), monobromophenols, were investigated by electron paramagnetic resonance (EPR). The results showed that three radicals, carbon-centered radical (C), hydrogen radical (H) and hydroxyl radical (OH), were generated from the direct irradiation of HPs. Compared to other substitutions, halogenated atom at para-position led to the highest production of these radicals which is in accordance with the energies calculated by density functional theory. Based on the analyses of the reactive species and corresponding intermediate adducts, the possible reaction pathways for these radicals were tentatively proposed. Dissolved organic matters (DOM) could enhance the photodegradation of HPs by directly affecting the radicals' formation, mainly due to generation of excited triplet DOM (DOM*). A positive correlation was found between the concentrations of hydrated electron and the steady state DOM* from different DOM. Our findings provided insights into environmental photochemical fate of HPs through their direct photolysis and will help more accurately understand their phototransformation mechanisms in the environment.