Evaluation of the role of superoxide radical as chain carrier for the formation of hydroxyl radical during ozonation

Superoxide radicals (O2•-) have been suggested as an important chain carrier in the radical chain reaction that promotes ozone (O3) decomposition to hydroxyl radicals (•OH) during ozonation. However, due to the difficulty in measuring transient O2•- concentrations, this hypothesis has not been verified under realistic ozonation conditions during water treatment. In this study, a probe compound was used in combination with kinetic modeling to evaluate the role of O2•- for O3 decomposition during ozonation of synthetic solutions with model promotors and inhibitors (methanol and acetate or tert-butanol) and natural waters (one groundwater and two surface waters). By measurement of the abatement of spiked tetrachloromethane (as a O2•- probe), the O2•- exposure during ozonation was determined. Based on the measured O2•- exposures, the relative contribution of O2•- to O3 decomposition, in comparison to OH-, •OH, and dissolved organic matter (DOM), was quantitatively evaluated using kinetic modeling. The results show that water compositions (e.g., the concentration of promotors and inhibitors, and the O3 reactivity of DOM) have a considerable effect on the extent of the O2•--promoted radical chain reaction during ozonation. In general, the reaction with O2•- accounted for ∼59‒70% and ∼45‒52% of the overall O3 decomposition during ozonation of the selected synthetic solutions and natural waters, respectively. This confirms that O2•- plays a critical role in promoting O3 decomposition to •OH. Overall, this study provides new insights on the controlling factors for ozone stability during ozonation processes.