Do We Appropriately Detect and Understand Singlet Oxygen Possibly Generated in Advanced Oxidation Processes by Electron Paramagnetic Resonance Spectroscopy?

Electron paramagnetic resonance (EPR) spectroscopy using sterically hindered amine is extensively applied to detect singlet oxygen (1O2) possibly generated in advanced oxidation processes. However, EPR-detectable 1O2 signals were observed in not only the 1O2-dominated hydrogen peroxide (H2O2)/hypochlorite (NaClO) reaction but surprisingly also the 1O2-absent Fe(II)/H2O2, UV/H2O2, and ferrate [Fe(VI)] process with even stronger intensities. By taking advantage of the characteristic reaction between 1O2 and 9,10-diphenyl-anthracene and near-infrared phosphorescent emission of 1O2, 1O2 was excluded in the Fe(II)/H2O2, UV/H2O2, and Fe(VI) process. The false detection of 1O2 was ascribed to the direct oxidation of hindered amine to piperidyl radical by reactive species [e.g., •OH and Fe(VI)/Fe(V)/Fe(IV)] via hydrogen transfer, followed by molecular oxygen addition (forming a piperidylperoxyl radical) and back reaction with piperidyl radical to generate a nitroxide radical, as evidenced by the successful identification of a piperidyl radical intermediate at 100 K and theoretical calculations. Moreover, compared to the highly oxidative species (e.g., •OH and high-valence Fe), the much lower reactivity of 1O2 and the profound nonradiative relaxation of 1O2 in H2O resulted it too selective and inefficient in organic contaminant destruction. This study demonstrated that EPR-based 1O2 detection could be remarkably misled by common oxidative species and thereby jeopardize the understandings on 1O2.

Surface-mediated periodate activation by nano zero-valent iron for the enhanced abatement of organic contaminants.

Periodate (PI)-based advanced oxidation processes have recently received increasing attentions. Herein, PI was readily activated by nano zero-valent iron (nZVI) and subsequently led to the enhanced oxidation of organic contaminants, with the removal performance of sulfadiazine (SDZ) in the nZVI/PI process even higher than that in the nZVI/peroxydisulfate process under identical conditions. Kinetic experiments indicated that the decay of SDZ was susceptible to the dosage of nZVI and PI, but was barely affected by pH values (4.0-7.0) under buffered conditions, suggesting the promising performance of the nZVI/PI process in a relatively wide pH range. Selective degradation of contaminants and 18O-isotope labeling assays collectively demonstrated that iodate radical (•IO3), high-valent iron-oxo species (Fe(IV)) and hydroxyl radical (•OH) were responsible for the abatement of organic contaminants. More importantly, due to the relatively weak steric hindrance effect of PI, PI easily adsorbed on the surface of nZVI and no iron leaching was detected throughout the reaction, implying that PI activation induced by nZVI was a surface-mediated process. Besides, PI was not transformed into harmful reactive iodine species. This study proposed an environmental-friendly approach for PI activation and shed new lights on the PI-based processes.

Highly selective oxidation of organic contaminants in the RuIII-activated peroxymonosulfate process: The dominance of RuVO species.

Ruthenium (RuIII)-activated peroxymonosulfate (the RuIII/PMS process) is one of the most efficient PMS-based advanced oxidation processes for the abatement of organic contaminants. Here we interestingly found that phenyl methyl sulfoxide (PMSO) was significantly oxidized to phenyl methyl sulfone (PMSO2) in the RuIII/PMS process at the pH range of 3.0-6.0, with the conversion ratio of ΔPMSO to ΔPMSO2 was close to 100%, which favored the dominance of high-valent ruthenium-oxo species (RuVO) instead of the widely-recognized radicals (i.e, hydroxyl radical and sulfate radical). Scavenging experiments further indicated that RuVO was unreactive to tert-butyl alcohol, but could be scavenged by methanol and dimethyl sulfoxide. Besides, sulfamethoxazole, acetaminophen, carbamazepine, diclofenac, 2,4,6-trichlorophenol were readily degraded in the RuIII/PMS process, but atrazine, ibuprofen, benzoic acid and 4-nitrobenzoic acid were barely removed, suggesting the high selectivity of RuVO species. This study enriched the understandings on the mechanism of RuIII-mediated PMS activation and the nature of RuVO species.

Enhanced Oxidation of Organic Contaminants by Iron(II)-Activated Periodate: The Significance of High-Valent Iron-Oxo Species.

Potassium periodate (PI, KIO4) was readily activated by Fe(II) under acidic conditions, resulting in the enhanced abatement of organic contaminants in 2 min, with the decay ratios of the selected pollutants even outnumbered those in the Fe(II)/peroxymonosulfate and Fe(II)/peroxydisulfate processes under identical conditions. Both 18O isotope labeling techniques using methyl phenyl sulfoxide (PMSO) as the substrate and X-ray absorption near-edge structure spectroscopy provided conclusive evidences for the generation of high-valent iron-oxo species (Fe(IV)) in the Fe(II)/PI process. Density functional theory calculations determined that the reaction of Fe(II) with PI followed the formation of a hydrogen bonding complex between Fe(H2O)62+ and IO4(H2O)-, ligand exchange, and oxygen atom transfer, consequently generating Fe(IV) species. More interestingly, the unexpected detection of 18O-labeled hydroxylated PMSO not only favored the simultaneous generation of ·OH but also demonstrated that ·OH was indirectly produced through the self-decay of Fe(IV) to form H2O2 and the subsequent Fenton reaction. In addition, IO4- was not transformed into the undesired iodine species (i.e., HOI, I2, and I3-) but was converted to nontoxic iodate (IO3-). This study proposed an efficient and environmental friendly process for the rapid removal of emerging contaminants and enriched the understandings on the evolution mechanism of ·OH in Fe(IV)-mediated processes.