Chaoting Guan

Transformation of Iodide by Carbon Nanotube Activated Peroxydisulfate and Formation of Iodoorganic Compounds in the Presence of Natural Organic Matter

In this study, we interestingly found that peroxydisulfate (PDS) could be activated by a commercial multiwalled carbon nanotube (CNT) material via a nonradical pathway. Iodide (I-) was quickly and almost completely oxidized to hypoiodous acid (HOI) in the PDS/CNT system over the pH range of 5-9, but the further transformation to iodate (IO3-) was negligible. A kinetic model was proposed, which involved the formation of reactive PDS-CNT complexes, and then their decomposition into sulfate anion (SO42-) via inner electron transfer within the complexes or by competitively reacting with I-. Several influencing factors (e.g., PDS and CNT dosages, and solution pH) on I- oxidation kinetics by this system were evaluated. Humic acid (HA) decreased the oxidation kinetics of I-, probably resulting from its inhibitory effect on the interaction between PDS and CNT to form the reactive complexes. Moreover, adsordable organic iodine compounds (AOI) as well as specific iodoform and iodoacetic acid were appreciably produced in the PDS/CNT/I- system with HA. These results demonstrate the potential risk of producing toxic iodinated organic compounds in the novel PDS/CNT oxidation process developed very recently, which should be taken into consideration before its practical application in water treatment.

Oxidation Kinetics of Bromophenols by Nonradical Activation of Peroxydisulfate in the Presence of Carbon Nanotube and Formation of Brominated Polymeric Products

This work demonstrated that bromophenols (BrPs) could be readily oxidized by peroxydisulfate (PDS) activated by a commercial carbon nanotube (CNT), while furfuryl alcohol (a chemical probe for singlet oxygen (1O2)) was quite refractory. Results obtained by radical quenching experiments, electron paramagnetic resonance spectroscopy, and Fourier transform infrared spectroscopy further confirmed the involvement of nonradical PDS-CNT complexes rather than 1O2. Bicarbonate and chloride ion exhibited negligible impacts on BrPs degradation by the PDS/CNT system, while a significant inhibitory effect was observed for natural organic matter. The oxidation of BrPs was influenced by solution pH with maximum rates occurring at neutral pH. Linear free energy relationships (LFERs) were established between the observed pseudo-first-order oxidation rates of various substituted phenols and the classical descriptor variables (i.e., Hammett constant σ+, and half-wave oxidation potential E1/2). Products analyses by liquid chromatography tandem mass spectrometry clearly showed the formation of hydroxylated polybrominated diphenyl ethers and hydroxylated polybrominated biphenyls on CNT surface. Their formation pathway possibly involved the generation of bromophenoxyl radicals from BrPs one-electron oxidation and their subsequent coupling reactions. These results suggest that the novel nonradical PDS/CNT oxidation technology is a good alternative for selectively eliminating BrPs with alleviating toxic byproducts in treated water effluent.

Factors affecting formation of deethyl and deisopropyl products from atrazine degradation in UV/H2O2 and UV/PDS

In this study, the formation of deethyl products (DEPs) (i.e., atrazine amide (Atra-imine) and deethylatrazine (DEA)) and deisopropyl product (i.e., deisopropylatrazine (DIA)) from parent atrazine (ATZ) degraded in UV/H2O2 and UV/PDS processes under various conditions was monitored. It was found that SO4˙− displayed a more distinctive preference to the ethyl function group of ATZ than HO˙, leading to the higher ratio of DEPs/DIA in UV/PDS system than that in UV/H2O2 system in pure water. The effects of water matrices (i.e., natural organic matter (NOM), carbonate/bicarbonate (HCO3−/CO32−), and chloride ions (Cl−)) on ATZ degradation as well as formation of DEPs and DIA were evaluated in detail. The degradation of ATZ by UV/PDS was significantly inhibited in the presence of NOM, HCO3−/CO32− or Cl−, because these components could competitively react with SO4˙− and/or HO˙ to generate lower reactive secondary radicals (i.e., organic radicals, carbonate radicals (CO3˙−) or reactive chlorine radicals (RCs)). The yields of these DEPs and DIA products from ATZ degradation were not impacted by NOM or HCO3−/CO32−, possibly due to the low reactivity of organic radicals and CO3˙− toward the side groups of ATZ. Howbeit, the increase of DIA yield companied with the decrease of DEPs yield was interestingly observed in the presence of Cl−, which was attributed to the promotion of Cl− at moderate concentration (mM range) for the conversion of SO4˙− into HO˙. Comparatively, in the UV/H2O2 process, NOM and HCO3−/CO32− exhibited a similar inhibitory effect on ATZ degradation, while the influence of Cl− was negligible. Differing from UV/PDS system, all these factors did not change DEPs and DIA yields in UV/H2O2 process. Moreover, it was confirmed that RCs had a greater selectivity but a lower reactivity on attacking the ethyl function group than that of SO4˙−. These findings were also confirmed by monitoring the degradation of ATZ as well as the formation of DEPs and DIA in three natural waters.

Comparative study on degradation of propranolol and formation of oxidation products by UV/H2O2 and UV/persulfate (PDS)

The frequent detection of propranolol, a widely used β-blocker, in wastewater effluents and surface waters has raised serious concern, due to its adverse effects on organisms. UV/hydrogen peroxide (UV/H2O2) and UV/persulfate (UV/PDS) processes are efficient in eliminating propranolol in various waters, but the formation of oxidation products in these processes, as well as the assessment of their toxicity, has not been systematically addressed. In this study, we identified and compared transformation products of propranolol produced by hydroxyl radical (•OH) and sulfate radical (SO4•-). The electrostatic attraction enhances the reaction between SO4•- and the protonated form of propranolol, while •OH shows non-selectivity toward both protonated and neutral propranolol species. The hydroxylation of propranolol by •OH occurs at either amine moiety or naphthalene group while SO4•- favors the oxidation of the electron-rich naphthalene group. Further oxidation by •OH and SO4•- results in ring-opening products. Bicarbonate and chloride exert no effect on propranolol degradation. The generation of CO3•- and Cl-containing radicals is favorable to oxidizing naphthalene group. The acute toxicity assay of Vibrio fischeri suggests that SO4•- generates more toxic products than •OH, while CO3•- and Cl-containing radicals produce similar toxicity as SO4•-. High concentrations of bicarbonate in UV/H2O2 increase the toxicity of treated solution.

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

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.

Effect of iodide on transformation of phenolic compounds by nonradical activation of peroxydisulfate in the presence of carbon nanotube: Kinetics, impacting factors, and formation of iodinated aromatic products

Our recent study has demonstrated that iodide (I-) can be easily and almost entirely oxidized to hypoiodous acid (HOI) but not to iodate by nonradical activation of peroxydisulfate (PDS) in the presence of a commercial carbon nanotube (CNT). In this work, the oxidation kinetics of phenolic compounds by the PDS/CNT system in the presence of I- were examined and potential formation of iodinated aromatic products was explored. Experimental results suggested that I- enhanced the transformation of six selected substituted phenols, primarily attributed to the generation of HOI that was considerably reactive toward these phenolic compounds. More significant enhancement was obtained at higher I- concentrations or lower pH values, while the change of PDS or CNT dosages exhibited a slight impact on the enhancing effect of I-. Product analyses with liquid chromatography tandem mass spectrometry clearly revealed the production of iodinated aromatic products when p-hydroxybenzoic acid (p-HBA, a model phenol) was treated by the PDS/CNT/I- system in both synthetic and real waters. Their formation pathways probably involved the substitution of HOI on aromatic ring of p-HBA, as well as the generation of iodinated p-HBA phenoxyl radicals and subsequent coupling of these radicals. Given the considerable toxicity and harmful effects of these iodinated aromatic products, particular attention should be paid when the novel PDS/CNT oxidation technology is applied for treatment of phenolic contaminants in iodide-containing waters.