Zhang Yanchang, Zhao Lin, Yang Yongkui, Sun Peizhe
School of Chemical Engineering and Technology, Tianjin University Tianjin 300350 People's Republic of China.
School of Environmental Science and Engineering, Tianjin University Tianjin 300350 People's Republic of China
RSC Adv. 2018 Oct 12;8(61):35062-35072. doi: 10.1039/c8ra04079f. eCollection 2018 Oct 10.
Degradation of ornidazole (ONZ) by nanoscale zero-valent iron (nZVI) particles was investigated for the first time in this work. The results showed that ONZ was almost completely degraded within 30 min by 0.1 g L nZVI at pH 5.8 and 25 °C. The effects of the nZVI dose, initial ONZ concentration, pH, and temperature on ONZ removal were systematically investigated, and removal of ONZ was followed by a pseudo-first-order kinetics model. Experimental results demonstrated that higher nZVI doses, lower initial ONZ concentrations, and lower pH levels could increase the pseudo-first-order rate constant ( ) of ONZ removal. While higher temperatures favored removal, the activation energy results suggested that mass transfer was the limiting step during the removal process. The possible effect of oxygen was ruled out by introducing hydroxyl radical scavengers into the experiment. The variation of ONZ concentrations and total organic carbon (TOC) contents in the solution indicated that adsorption was not the main mechanism. The possibility that precipitation was the main mechanism was also excluded by the results for the change in pH and effect of pH. The characterization of nZVI before and after the reaction indicated that ONZ was reduced on the surface of nZVI, which was the main mechanism. Three intermediates and two final products were detected based on the results of UV-vis and high performance liquid chromatography/mass spectrometry (HPLC-MS) analyses. Dechlorination, nitro reduction, N-denitration, and cleavage were all involved in the entire reaction process, and therefore a complicated potential degradation pathway was proposed.
本研究首次对纳米零价铁(nZVI)颗粒降解奥硝唑(ONZ)进行了调查。结果表明,在pH 5.8和25℃条件下,0.1 g/L的nZVI可在30分钟内将ONZ几乎完全降解。系统研究了nZVI剂量、初始ONZ浓度、pH值和温度对ONZ去除的影响,并采用伪一级动力学模型跟踪ONZ的去除情况。实验结果表明,较高的nZVI剂量、较低的初始ONZ浓度和较低的pH值可提高ONZ去除的伪一级速率常数( )。虽然较高的温度有利于去除,但活化能结果表明传质是去除过程中的限制步骤。通过在实验中引入羟基自由基清除剂排除了氧的可能影响。溶液中ONZ浓度和总有机碳(TOC)含量的变化表明吸附不是主要机制。pH值变化和pH值影响的结果也排除了沉淀是主要机制的可能性。反应前后nZVI的表征表明ONZ在nZVI表面被还原,这是主要机制。根据紫外可见光谱和高效液相色谱/质谱(HPLC-MS)分析结果检测到三种中间体和两种最终产物。整个反应过程涉及脱氯、硝基还原、N-脱硝化和裂解,因此提出了一条复杂的潜在降解途径。