Occurrence of unknown reactive species in UV/H₂O₂ system leading to false interpretation of hydroxyl radical probe reactions

The UV/H₂O₂ process is a benchmark advanced oxidation process (AOP) that in situ generates highly reactive and nonselective hydroxyl radical (^•OH) to oxidatively destroy a wide range of organic compounds. Accurately quantifying the concentration of short-lived ^•OH is essential to predict process performance, optimize the operation parameters, and compare with other process options. The ^•OH concentration is typically measured using organic probe molecules that react with ^•OH but not with other oxidants. In the extremely well-characterized UV/H₂O₂ system in which ^•OH is proven to be the dominant oxidant, using photolysis-resistant probes such as benzoic acid and its derivatives is a widely agreed and practiced norm. We herein report that certain ^•OH probe compounds can be degraded in UV/H₂O₂ system by unknown reactive species that has not been reported in the past. Several common organic probes, particularly p-substituted benzoic acid compounds (i.e., p-hydroxybenzoic acid, p-chlorobenzoic acid, and p-phthalic acid), were found to be vulnerable to attack by the unknown reactive species, leading to false quantification of ^•OH concentration under high radical scavenging conditions. Lines of evidence obtained from a series of ^•OH scavenging experiments performed under various conditions (i.e., different concentrations of H₂O₂, ^•OH probe compounds, and dissolved oxygen) point toward excited state H₂O₂. The results from this study suggest the importance of using appropriate ^•OH probe compounds in mechanistic studies and needs for considering the unidentified role of excited state of H₂O₂ on the UV/H₂O₂ process and related AOPs.