Quantitative probing of reactive oxygen species and their selective degradation on contaminants in peroxymonosulfate-based process enhanced by picolinic acid

Abstract

The processes of Fe(III) activated peroxymonosulfate (PMS) in degrading contaminants have been extensively studied. Herein, a biodegradable chelating agent, picolinic acid (PICA), was introduced to the PMS/Fe(III) process to improve the reaction efficiency. The emphases of this study were placed on the quantification of steady-state concentrations of reactive oxygen species (ROS). Experiments presented that five types of ROS, including Fe(IV), SO4•−, HO•, 1O2 and O2•− coexisted in this system. Four typical probe compounds were used to quantify the steady-state concentration of ROS under different variables. The steady-state concentration of Fe(IV) ([Fe(IV)]ss) was 3–5 orders of magnitude higher than that of other ROS, followed by 1O2 and SO4•−, whereas HO• had the lowest concentration. The reaction between PMS and PICA was first explored in our study and results showed that 1O2 and O2•− would form in this reaction. Owing to the hybrid oxidation by multiple ROS, this system showed high oxidation capacity, and could effectively degrade a variety of pollutants. The contributions of ROS to the alleviation of pollutants varied depending on their concentrations and specific reactivity of substrates. Generally, organic contaminants with phenol structures were prone to react with Fe(IV). Overall, this study compared the steady-state concentrations of different ROS and revealed the intrinsic ROS formation mechanisms.