Kinetic Consideration of Photochemical Formation and Decay of Superoxide Radical in Dissolved Organic Matter Solutions.

The photochemical formation and decay rates of superoxide radical ions (O2•-) in irradiated dissolved organic matter (DOM) solutions were directly determined by the chemiluminescent method. Under irradiation, uncatalyzed and catalyzed O2•- dismutation account for ∼25% of the total O2•- degradation in air-saturated DOM solutions. Light-induced O2•- loss, which does not produce H2O2, was observed. Both the O2•- photochemical formation and light-induced loss rates are positively correlated with the electron-donating capacities of the DOM, suggesting that phenolic moieties play a dual role in the photochemical behavior of O2•-. In air-saturated conditions, the O2•- quantum yields of 12 DOM solutions varied in a narrow range, from 1.8 to 3.3‰, and the average was (2.4 ± 0.5)‰. The quantum yield of O2•- nonlinearly increased with increasing dissolved oxygen concentration. Therefore, the quantum yield of one-electron reducing intermediates, the precursor of O2•-, was calculated as (5.0 ± 0.4)‰. High-energy triplets (3DOM*, ET > 200 kJ mol-1) and 1O2 quenching experiments indicate that 3DOM* and 1O2 play minor roles in O2•- production. These results are useful for predicting the photochemical formation and decay of O2•- in sunlit surface waters.