Assessing the Contribution of Free Hydroxyl Radical in Organic Matter-Sensitized Photohydroxylation Reactions

Photochemical formation of reactive oxygen species from dissolved organic matter (DOM) is incompletely understood, especially in the case of hydroxyl radical (center dot OH) production. Many studies have used various probes to detect photochemically produced center dot OH from DOM, but the fundamental reactions of these probes are not necessarily specific for free center dot OH and may also detect lower-energy hydroxylation agents. In this study, two tests were applied that have previously been used as a diagnostic for the presence of free center dot OH: methane quenching of center dot OH and hydroxybenzoic acid (hBZA) product yields. Upon application of these two tests to a set of five DOM isolates, it was found that methane quenching and the hBZA ratio results were not necessarily consistent. Overall, the results provide compelling evidence that all isolates studied photochemically produce free center dot OH. The hydroxylating acitivity of Elliot Soil Humic Acid and Pony Lake Fulvic Acid, however, also had a significant contribution from a photochemically generated hydroxylating agent that is lower in energy than free center dot OH. Catalase quenching experiments were conducted to assess whether hydrogen peroxide was the immediate precursor to hydroxyl in these systems. In all cases, catalase addition slowed photohydroxylation of terephthalate, but the contribution of hydrogen peroxide photolysis was determined to be less than 50%.