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Is Sulfate Radical Really Generated from Peroxydisulfate Activated by Iron(II) for Environmental Decontamination?

Author:
Wang, Zhen, Jiang, Jin, Pang, Suyan, Zhou, Yang, Guan, Chaoting, Gao, Yuan, Li, Juan, Yang, Yi, Qiu, Wei, Jiang, Chengchun
Source:
Environmental science & technology 2018 v.52 no.19 pp. 11276-11284
ISSN:
1520-5851
Subject:
alcohols, biphenyl, decontamination, hydrogen peroxide, hydroxyl radicals, iron, kinetics, models, oxidation, pH, pollution, sulfates
Abstract:
It is well documented that the traditional Fenton reagent (i.e., the combination of Fe(II) and H₂O₂) produces hydroxyl radical (•OH) under acidic conditions, while at near-neutral pH the reactive intermediate converts to ferryl ion (Fe(IV)) that can oxidize sulfoxides to produce corresponding sulfones, markedly differing from their •OH-induced products. However, it remains unclear whether Fe(IV) is generated in the Fe(II) activated peroxydisulfate (PDS) process, where sulfate radical (SO₄•–) is long recognized as the dominant intermediate in literature. Here we demonstrated that SO₄•– oxidized methyl phenyl sulfoxide (PMSO, a model sulfoxide) to produce biphenyl compounds rather than methyl phenyl sulfone (PMSO₂). Interestingly, the formation of PMSO₂ was observed when PMSO was treated by the Fe(II)/PDS system over a wide pH range, and the yields of PMSO₂ were quantified to be ∼100% at acidic pH 3–5. The identification of Fe(IV) in the Fe(II)/PDS system could also reasonably explain the literature results on alcohol scavenging effect and ESR spectra analysis. Further, a Fe(IV)-based kinetic model was shown to accurately simulate the experimental data. This work urges re-evaluation of the Fe(II)/PDS system for environmental decontamination, given that Fe(IV) would have different reactivity toward environmental contaminants compared with SO₄•– and/or •OH.
Agid:
6145968