KU Leuven, Department of Chemical Engineering, Process and Environmental Technology Lab, J. De Nayerlaan 5, B-2860 Sint-Katelijne-Waver, Belgium; KU Leuven, Department of Pharmaceutical and Pharmacological Sciences, Pharmaceutical Analysis, Herestraat 49, B-3000 Leuven, Belgium.
KU Leuven, Department of Pharmaceutical and Pharmacological Sciences, Pharmaceutical Analysis, Herestraat 49, B-3000 Leuven, Belgium.
Sci Total Environ. 2019 Oct 20;688:65-74. doi: 10.1016/j.scitotenv.2019.06.210. Epub 2019 Jun 15.
Diclofenac (DCF) is a non-steroidal anti-inflammatory drug which is frequently detected in the aqueous environment. The synergistic treatment using sulfite and UV irradiation is proposed to be one of the most effective advanced reduction processes (ARPs) to degrade refractory contaminants. This paper systematically investigated the performance and mechanism of DCF degradation by sulfite/UV ARP under various conditions. A significant enhancement in degradation efficiency of DCF was exhibited via sulfite/UV ARP compared with direct UV photolysis, which is primarily due to the generation of reductive radicals (e and H). This process was well described by a pseudo first-order kinetic model with a rate constant of 0.154 min. The influence of solution pH, sulfite dosage, initial DCF concentration and UV intensity were evaluated. Results revealed that DCF more favorably reacted with H in an acidic environment than with e under alkaline conditions. A positive impact on the DCF decomposition was observed with increasing sulfite dosage, but with an inhibiting trend at high sulfite concentrations. The degradation rate constant was accelerated by increasing the UV intensity, while decreased by promoting the initial DCF concentration. Degradation mechanisms at different pH levels revealed that the reduction reactions were induced by e at pH 9.2, and dominated by H at pH 6.0. Complete dechlorination was readily achieved with all chlorine atoms in DCF released as chloride ions under sulfite/UV ARP, which may lead to a decreased toxicity of the degradation products. This observation emphasized the advantages of sulfite/UV ARP on DCF degradation, in comparison with that under direct UV photolysis.
双氯芬酸(DCF)是一种在水环境中经常被检测到的非甾体抗炎药。亚硫酸盐和紫外光辐照的协同处理被提议为降解难处理污染物的最有效高级还原过程(ARP)之一。本文系统地研究了亚硫酸盐/紫外光 ARP 在各种条件下对 DCF 降解的性能和机制。与直接紫外光解相比,亚硫酸盐/紫外光 ARP 显著提高了 DCF 的降解效率,这主要是由于还原性自由基(e 和 H)的产生。该过程通过拟一级动力学模型很好地描述,速率常数为 0.154 min。评估了溶液 pH 值、亚硫酸盐用量、初始 DCF 浓度和紫外光强度的影响。结果表明,DCF 在酸性环境中比在碱性条件下更有利于与 H 反应,而不是与 e 反应。随着亚硫酸盐用量的增加,对 DCF 分解有积极的影响,但在高亚硫酸盐浓度下有抑制趋势。降解速率常数随着紫外光强度的增加而加速,而随着初始 DCF 浓度的增加而降低。在不同 pH 值下的降解机制表明,在 pH 值为 9.2 时,还原反应是由 e 诱导的,而在 pH 值为 6.0 时,则由 H 主导。在亚硫酸盐/紫外光 ARP 下,所有氯原子都以氯离子的形式从 DCF 中释放出来,从而很容易实现完全脱氯,这可能会降低降解产物的毒性。与直接紫外光解相比,这一观察结果强调了亚硫酸盐/紫外光 ARP 在 DCF 降解方面的优势。