Environmental implications of superoxide radicals: From natural processes to engineering applications

The roles of superoxide radical (O₂^•-) in the domains of physiological, physical, and material chemistry are becoming increasingly recognized. Although extensive efforts have been directed to understand O₂^•- functions in diverse aquatic systems, there is a lack of systematic and in-depth review for its kinetics and mechanisms in various environmental scenarios. This review aims to bridge this gap through discussion of O₂^•- generation pathways under both natural and controlled conditions. The merits and limitations of the generation and detection methods under various conditions are compared, with emphasis on different approaches for the determination of O₂^•--triggered reaction kinetics. We summarize the reaction rate constants of O₂^•- with organic contaminants covering a wide diversity of structures and reactivity. The comparison indicates that O₂^•- exhibits weak reactivity with most contaminants and lacks selectivity towards compounds with different functional groups, except with quinones which exhibit higher reactivity compared to non-quinones. Further, the reaction mechanisms, namely single electron transfer, nucleophilic substitution, hydrogen atom abstraction, and radical-adduct formation, are critically evaluated. Various environmental implications of O₂^•- are highlighted including maintenance of biogeochemical iron cycle, synthesis of nanoparticles for antibacterial purposes, desorption of contaminants from heterogeneous interfaces, and synergetic degradation of contaminants.