Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems

Peroxymonosulfate (PMS, HSO₅^-) is a widely-used disinfectant and oxidant in environmental remediation. It was deemed that PMS reacted with chloride (Cl^-) to form free chlorine during water purification. Here, we demonstrated that singlet oxygen (¹O₂) was efficiently generated from PMS and Cl^- interaction. Mechanism of ¹O₂ formation was uniquely verified by the reaction of HSO₅^- and chlorine molecule (Cl₂) and the oxygen atoms in ¹O₂ deriving from the peroxide group of HSO₅^- were revealed. Density functional theory calculations determined that the reaction of HSO₅^- and Cl₂ was thermodynamically favorable and exergonic at 37.8 kcal/mol. Quite intriguingly, ¹O₂ was generated at a higher yield (1.5 × 10⁵ M ^- 1 s ^- 1) than in the well-known reaction of H₂O₂ with Cl₂ (35 M ^- 1 s ^- 1). Besides chlorine, ¹O₂ formed in PMS-Cl^- interaction dominated the degradation of micropollutants, also it substantially enhanced the damage of deoxynucleoside in DNA, which were beneficial to micropollutant oxidation and pathogen disinfection. The contribution of ¹O₂ for carbamazepine degradation was enhanced at higher Cl^- level and lower pH, and reached 96.3% at pH 4.1 and 5 min. Natural organic matter (NOM) was a sink for chlorine, thereby impeding ¹O₂ formation to retard carbamazepine degradation. ¹O₂ also played important roles (48.3 - 63.5%) on the abatement of deoxyguanosine and deoxythymidine at pH 4.1 and 10 min in PMS/Cl^-. On the other hand, this discovery also alerted the harm of ¹O₂ for human health as it can be formed during the interaction of residual PMS in drinking water/swimming pools and the high-level Cl^- in human bodies.