Reaction of FeaqII with Peroxymonosulfate and Peroxydisulfate in the Presence of Bicarbonate: Formation of FeaqIV and Carbonate Radical Anions

Aswin Kottapurath Vijay, Vered Marks, Amir Mizrahi, Yinghao Wen, Xingmao Ma, Virender K. Sharma, Dan Meyerstein

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

Many advanced oxidation processes (AOPs) use Fenton-like reactions to degrade organic pollutants by activating peroxymonosulfate (HSO5-, PMS) or peroxydisulfate (S2O82-, PDS) with Fe(H2O)62+ (FeaqII). This paper presents results on the kinetics and mechanisms of reactions between FeaqII and PMS or PDS in the absence and presence of bicarbonate (HCO3-) at different pH. In the absence of HCO3-, FeaqIV, rather than the commonly assumed SO4•-, is the dominant oxidizing species. Multianalytical methods verified the selective conversion of dimethyl sulfoxide (DMSO) and phenyl methyl sulfoxide (PMSO) to dimethyl sulfone (DMSO2) and phenyl methyl sulfone (PMSO2), respectively, confirming the generation of FeaqIV by the FeaqII-PMS/PDS systems without HCO3-. Significantly, in the presence of environmentally relevant concentrations of HCO3-, a carbonate radical anion (CO3•-) becomes the dominant reactive species as confirmed by the electron paramagnetic resonance (EPR) analysis. The new findings suggest that the mechanisms of the persulfate-based Fenton-like reactions in natural environments might differ remarkably from those obtained in ideal conditions. Using sulfonamide antibiotics (sulfamethoxazole (SMX) and sulfadimethoxine (SDM)) as model contaminants, our study further demonstrated the different reactivities of FeaqIV and CO3•- in the FeaqII-PMS/PDS systems. The results shed significant light on advancing the persulfate-based AOPs to oxidize pollutants in natural water.

Original languageEnglish
Pages (from-to)6743-6753
Number of pages11
JournalEnvironmental Science and Technology
Volume57
Issue number16
DOIs
StatePublished - 25 Apr 2023

Keywords

  • advanced oxidation processes
  • carbonate radical anion
  • fenton-like reactions
  • ferryl ion
  • persulfate radical anion

ASJC Scopus subject areas

  • General Chemistry
  • Environmental Chemistry

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