Non-Singlet Oxygen Kinetic Solvent Isotope Effects in Aquatic Photochemistry

The kinetic solvent isotope effect (KSIE) is typically utilized in environmental photochemistry to elucidate whether a compound is susceptible to photooxidation by singlet oxygen (¹O₂), due to its known difference in lifetime in water (H₂O) versus heavy water (D₂O). Here, the overall indirect photodegradation rates of diarylamines in the presence of dissolved organic matter (DOM) were enhanced in D₂O to a greater extent than expected based on their reactivity with ¹O₂. For each diarylamine, the relative contribution of reaction with ¹O₂ to the observed KSIE was determined from high resolution data of ¹O₂ lifetimes by time-resolved infrared luminescence spectroscopy. The additional enhancement in D₂O beyond reaction with ¹O₂ contributed significantly to the observed KSIE for diarylamines (8-65%) and diclofenac (100%). The enhancement was ascribed to slower reduction of transient radical species of the diarylamines due to H/D exchange at DOM's phenolic antioxidant moieties. A slower second-order reaction rate constant with a model antioxidant was verified for mefenamic acid radicals using transient absorption spectroscopy. Changes in lifetime and reactivity with triplet sensitizers were not responsible for the additional KSIE. Other pollutants with quenchable radical intermediates may also be susceptible to such an additional KSIE, which has to be considered when using the KSIE as a diagnostic tool.