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It is well documented that the traditional Fenton reagent (i.e., the combination of Fe(II) and HO) 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 (SO) is long recognized as the dominant intermediate in literature. Here we demonstrated that SO oxidized methyl phenyl sulfoxide (PMSO, a model sulfoxide) to produce biphenyl compounds rather than methyl phenyl sulfone (PMSO). Interestingly, the formation of PMSO was observed when PMSO was treated by the Fe(II)/PDS system over a wide pH range, and the yields of PMSO 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 SO and/or OH.

The reactions between peroxymonosulfate (PMS) and quinones were investigated for the first time in this work, where benzoquinone (BQ) was selected as a model quinone. It was demonstrated that BQ could efficiently activate PMS for the degradation of sulfamethoxazole (SMX; a frequently detected antibiotic in the environments), and the degradation rate increased with solution pH from 7 to 10. Interestingly, quenching studies suggested that neither hydroxyl radical (•OH) nor sulfate radical (SO4•-) was produced therein. Instead, the generation of singlet oxygen (1O2) was proved by using two chemical probes (i.e., 2,2,6,6-tetramethyl-4-piperidinol and 9,10-diphenylanthracene) with the appearance of 1O2 indicative products detected by electron paramagnetic resonance spectrometry and liquid chromatography mass spectrometry, respectively. A catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PMS and BQ and the subsequent decomposition of this intermediate into 1O2. Accordingly, a kinetic model was developed, and it well described the experimental observation that the pH-dependent decomposition rate of PMS was first-order with respect to BQ. These findings have important implications for the development of novel nonradical oxidation processes based on PMS, because 1O2 as a moderately reactive electrophile may suffer less interference from background organic matters compared with nonselective •OH and SO4•-.

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