Possible formation of long-lived photo-oxidants by photolysis of organic matter phenols in sunlit waters

Photodegradation in sunlit waters is a major process of contaminant abatement, yet underlying chemical processes in the presence of dissolved organic matter are poorly known. Long-lived photo-oxidants are reactive species formed when the chromophoric dissolved organic matter absorbs sunlight, and they are involved in the degradation of contaminants. Previous works identified long-lived photo-oxidants with phenoxy radicals, which could be formed upon oxidation of natural phenols by the excited triplet states of chromophoric dissolved organic matter. Here, we generated reactive phenoxy radicals by direct ultraviolet-A photolysis of 2-nitrophenol and 4-nitrophenol. We measured the second-order rate constants for reaction of these phenoxy radicals with 2,4,6-trimethylphenol, a model electron-rich phenol. Results show rate constants of 9.39 × 10⁸(M⁻¹s⁻¹) for the 2-nitrophenoxyl radical, and 1.56 × 10⁸(M⁻¹s⁻¹) for the 4-nitrophenoxyl radical. These values are slightly lower than the typical rate constant of the reaction between 2,4,6-trimethylphenol and the excited triplet states of chromophoric dissolved organic matter, of 3 × 10⁹(M⁻¹s⁻¹). This means that 2,4,6-trimethylphenol would not be degraded to comparable extents by the excited triplet states of chromophoric dissolved organic matter and by long-lived photo-oxidants, if long-lived photo-oxidants were generated solely by the triplet states of chromophoric dissolved organic matter. Overall, findings suggest the occurrence of new pathway involving the direct photolysis of organic matter phenols that generates long-lived photo-oxidants.