Shiqing Zhou

Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (kobs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4−••) were identified to be responsible for OXC degradation and SO4−• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

Degradation of carbamazepine by UV/chlorine advanced oxidation process and formation of disinfection by-products

Pharmaceuticals in water are commonly found and are not efficiently removed by current treatment processes. Degradation of antiepileptic drug carbamazepine (CBZ) by UV/chlorine advanced oxidation process was systematically investigated in this study. The results showed that the UV/chlorine process was more effective at degrading CBZ than either UV or chlorination alone. The CBZ degradation followed pseudo-first order reaction kinetics, and the degradation rate constants (kobs) were affected by the chlorine dose, solution pH, and natural organic matter concentration to different degrees. Degradation of CBZ greatly increased with increasing chlorine dose and decreasing solution pH during the UV/chlorine process. Additionally, the presence of natural organic matter in the solution inhibited the degradation of CBZ. UV photolysis, chlorination, and reactive species (hydroxyl radical •OH and chlorine atoms •Cl) were identified as responsible for CBZ degradation in the UV/chlorine process. Finally, a degradation pathway for CBZ in the UV/chlorine process was proposed and the formation potentials of carbonaceous and nitrogenous disinfection by-products were evaluated. Enhanced formation of trichloroacetic acid, dichloroacetonitrile, and trichloronitromethane precursors should be considered when applying UV/chlorine advanced oxidation process to drinking water.

Removal of 2-MIB and geosmin by electrogenerated persulfate: Performance, mechanism and pathways

In this study, the degradation of 2-methylisoborneol (2-MIB) and geosmin (GSM) was evaluated by electrochemical oxidation (EO) using boron-doped diamond (BDD) electrode. Both 2-MIB and GSM could be degraded efficiently in sulfate electrolyte compared to inert nitrate or perchlorate electrolytes, implying that in-situ generated persulfate may be responsible for contaminants degradation. The observed linear relationship between 2-MIB (GSM) degradation rates and persulfate generation rates further proved that the in-situ generated persulfate enhanced 2-MIB (GSM) degradation. Moreover, a divided electrolytic cell was employed to investigate the effect of cathodic reactions on contaminants degradation and persulfate generation, and results confirmed that both anodic and cathodic reactions participated in 2-MIB (GSM) degradation. High current density and low solution pH were found to be favorable for 2-MIB and GSM degradation. The degradation intermediates were identified and the possible pathways of 2-MIB and GSM degradation were proposed. This study indicated that the EO process with BDD anode could be considered as a potential alternative for the removal of 2-MIB and GSM.

Enhanced degradation of Orange G by permanganate with the employment of iron anode

Iron anode was employed to enhance the degradation of Orange G (OG) by permanganate (EC/KMnO4). Continuously generated Fe2+ from iron anode facilitated the formation of fresh MnO2, which plays a role in catalyzing permanganate oxidation. The EC/KMnO4 system also showed a better performance to remove OG than Fe2+/KMnO4, indicating the importance of in situ formed fresh MnO2. Besides, the effects of applied current, KMnO4 dosage, solution pH, and natural organics were evaluated and results demonstrated that high current and oxidant dosage are favorable for OG removal. And the application of iron anode has a promoting effect on the KMnO4 oxidation over a wide pH range (5.0–9.0), while the Fe2+/KMnO4 process does not. For natural organics, its presence could inhibit OG removal due to its competitive role. And the promoting effect of OG removal by the EC/KMnO4 process in natural water was confirmed. At last, the EC/KMnO4 process showed a satisfying performance on the decolorization and mineralization of OG. This study provides a potential technology to enhance permanganate oxidation and broadens the knowledge of azo dye removal.

Electrochemical inactivation of Microcystis aeruginosa using BDD electrodes: Kinetic modeling of microcystins release and degradation

Electrochemical inactivation of cyanobacteria using boron-doped diamond (BDD) electrode were comprehensively investigated in this study. The pulse amplitude modulated (PAM) fluorometry, flow cytometry, and confocal laser scanning microscopy (CLSM) were used to characterize the photosynthetic capacity and cell integrity of Microcystis aeruginosa. Persulfate is in-situ generated and activated during the process and responsible for the inactivation of M. aeruginosa. The inactivation efficiency increases along with the increase of applied currents. Additionally, a kinetic model based on a sequence of two consecutive irreversible first-order processes was developed to simulate the release and degradation of microcystins (MCLR). The model was able to successfully predict the concentration of extracellular, intracellular and total MCLR under different applied currents and extended exposure time.

Degradation of dyes by peroxymonosulfate activated by ternary CoFeNi-layered double hydroxide: Catalytic performance, mechanism and kinetic modeling

Ternary CoFeNi-layered double hydroxide (CoFeNi-LDH) was synthesized and initially applied to activate peroxymonosulfate (PMS) for the degradation of Congo red (CR) and Rhodamine B (RhB). The results show that the CoFeNi-LDH/PMS system can efficiently degrade nearly 100% of 20 mg/L CR or 20 mg/L RhB within 6- and 10-min reaction times, respectively. And the catalyst exhibits higher degradation efficiency on CR than on RhB under identical conditions, which is confirmed by electron clouds of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) performed by DFT calculations. Quenching tests reveal that SO4- is the dominant active species participating in the degradation process. Mechanism investigation demonstrates that Co(II)-Co(III)-Co(II) cycle is responsible for activating PMS to generate radicals for dyes degradation. A dynamic kinetic model is successfully developed to simulate the concentration profiles of CR and RhB degradation in CoFeNi-LDH/PMS system. The empirical second order rate constants between SO4- and CR (kSO4-/CR), HO and CR (kOH/CR), SO4- and RhB (kSO4-/RhB), HO and RhB (kHO/RhB) are determined to be 2.47 × 107, 3.44 × 106, 8.39 × 106 and 2.62 × 107 M-1s-1, respectively. In addition, toxic assessment using ECOSAR program suggests that the overall toxicity of CR and RhB decreased after treatment with CoFeNi-LDH/PMS system. Repeating tests and application of CoFeNi-LDH in different water sources give us adequate confidence that the as-synthesized CoFeNi-LDH is favorable for the purification of dye-contaminanted waters in practical.

Oxidation of microcystin-LR via activation of peroxymonosulfate using ascorbic acid: Kinetic modeling and toxicity assessment

Advanced oxidation processes (AOPs) have been widely used for the destruction of organic contaminants in the aqueous phase. In this study, we introduce an AOP on activated peroxymonosulfate (PMS) by using ascorbic acid (H2A) to generate sulfate radicals (SO4•-). Sulfate radicals, hydroxyl radicals (HO•), and ascorbyl radicals (A•-) were found using electron spin resonance (ESR). But we found A•- is negligible in the degradation of microcystin-LR (MCLR) due to its low reactivity. We developed a first-principles kinetic model to simulate the MCLR degradation and predict the radical concentrations. The MCLR degradation rate decreased with increasing pH. The scavenging effect of natural organic matter (NOM) on SO4•- was relatively small compared to that for HO•. Considering both energy consumption and MCLR removal, the optimal H2A and PMS doses for H2A/PMS process were determined at 1.0 × 10-6 M and 1.6 × 10-5 M, respectively. In addition, we determined the toxicity using the protein phosphatase 2A (PP2A) test and the results showed that MCLR was readily detoxified and its oxidation byproducts were not hepatotoxic. Overall, our work provides a new type of AOP and a promising, efficient, and environmental-friendly method for removing microcystins in algae-laden water.

Impact of Chloride Ions on UV/H2O2 and UV/Persulfate Advanced Oxidation Processes

Chloride ion (Cl-) is one of the most common anions in the aqueous environment. A mathematical model was developed to determine and quantify the impact of Cl- on the oxidization rate of organic compounds at the beginning stage of the UV/persulfate (PS) and UV/H2O2 processes. We examined two cases for the UV/PS process: (1) when the target organic compounds react only with sulfate radicals, the ratio of the destruction rate of the target organic compound when Cl- is present to the rate when Cl- is not present (designated as rRCl-/ rR) is no larger than 1.942%; and (2) when the target organic compounds can react with sulfate radicals, hydroxyl radicals and chlorine radicals, rRCl-/ rR, can be no larger than 60%. Hence, Cl- significantly reduces the organic destruction rate in the UV/PS process. In the UV/H2O2 process, we found that Cl- has a negligible effect on the organic-contaminant oxidation rate. Our simulation results agree with the experimental results very well. Accordingly, our mathematical model is a reliable method for determining whether Cl- will adversely impact organic compounds destruction by the UV/PS and UV/H2O2 processes.