Synergistic effects of ozone/peroxymonosulfate for isothiazolinone biocides degradation: Kinetics, synergistic performance and influencing factors
2022
Yang, Zheng-Wei | Wang, Wen-Long | Lee, Min-Yong | Wu, Qian-Yuan | Guan, Yun-Tao
Synergistic effects of ozone (O₃) and peroxymonosulfate (PMS, HSO₅⁻) for isothiazolinone biocides degradation was studied. The synergistic ozonation process (O₃/PMS) increased the efficiency of methyl-isothiazolinone (MIT) and chloro-methyl-isothiazolinone (CMIT) degradation to 91.0% and 81.8%, respectively, within 90 s at pH 7.0. This is 30.6% and 62.5% higher than the corresponding ozonation efficiency, respectively. Total radical formation value (Rcₜ,R) for the O₃/PMS process was 24.6 times that of ozonation alone. Calculated second-order rate constants for the reactions between isothiazolinone biocides and ▪ (kSO₄₋,MIT and kSO₄₋,CMIT) were 8.15 × 10⁹ and 4.49 × 10⁹ M⁻¹ s⁻¹, respectively. Relative contributions of O₃, hydroxyl radical (OH) and ▪ oxidation to MIT and CMIT removal were estimated, which were 15%, 45%, and 40% for O₃, OH and ▪ oxidation to MIT, and 1%, 67%, and 32% for O₃, OH and ▪ oxidation to CMIT at pH 7.0, respectively. Factors influencing the O₃/PMS process, namely the solution pH, chloride ions (Cl⁻), and bicarbonate (HCO₃⁻), were evaluated. Increasing the solution pH markedly accelerated O₃ decay and OH and ▪ formation, thus weakening the relative contribution of O₃ oxidation while enhancing that of OH and ▪. Cl⁻ had a negligible effect on MIT and CMIT degradation. Under the dual effect of bicarbonate (HCO₃⁻) as inhibitor and promoter, low concentrations (1–2 mM) of bicarbonate weakly promoted MIT and CMIT degradation, while high concentrations (10–20 mM) induced strong inhibition. Lastly, oxidation performance of O₃ and O₃/PMS processes for MIT and CMIT degradation in different water matrices was compared.
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