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过氧乙酸在磷酸盐诱导下对双氯芬酸的降解:动力学、影响因素及机制。

Phosphate-induced activation of peracetic acid for diclofenac degradation: Kinetics, influence factors and mechanism.

机构信息

Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu, 611756, China.

Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu, 611756, China; School of Architecture and Civil Engineering, Chengdu University, 610106, China.

出版信息

Chemosphere. 2022 Jan;287(Pt 4):132396. doi: 10.1016/j.chemosphere.2021.132396. Epub 2021 Sep 28.

Abstract

Activating peroxides to produce active substances is the key to advanced oxidation processes (AOPs), but this usually requires energy or is accompanied by additional contaminants. In this study, diclofenac (DCF) was effectively removed by peracetic acid (PAA) in phosphate buffer (PBS). According to the results of radical scavenging experiments and electron paramagnetic resonance (EPR), hydroxyl radical (•OH) and organic radicals (i.e., CHC(=O)OO• and CHC(=O)O•) generated from PBS-activated PAA might be the dominant reactive species responsible for DCF degradation. At neutral pH, PBS/PAA system exhibited the best degradation efficiency on DCF. Presence of NO, SO and Cl had little effect on the removal of DCF, while HCO and natural organic matter (NOM) significantly inhibited DCF degradation in PBS/PAA system, resulting in the lower degradation efficiency of DCF in natural waters than that in ultrapure water. Finally, four possible degradation pathways, including hydroxylation, formylation, dehydrogenation and dechlorination, were proposed based on the detected reaction products. This study suggests that PBS used to control solution pH should be applied cautiously in PAA-based AOPs.

摘要

过氧化物的活化生成活性物质是高级氧化过程(AOPs)的关键,但这通常需要能量或伴随着额外的污染物。在本研究中,过氧乙酸(PAA)在磷酸盐缓冲液(PBS)中有效地去除了双氯芬酸(DCF)。根据自由基清除实验和电子顺磁共振(EPR)的结果,PBS 活化 PAA 生成的羟基自由基(•OH)和有机自由基(即,CHC(=O)OO•和 CHC(=O)O•)可能是导致 DCF 降解的主要反应性物质。在中性 pH 下,PBS/PAA 体系对 DCF 的降解效率最高。NO、SO 和 Cl 的存在对 DCF 的去除几乎没有影响,而 HCO 和天然有机物(NOM)则显著抑制了 PBS/PAA 体系中 DCF 的降解,导致 DCF 在天然水中的降解效率低于超纯水中。最后,根据检测到的反应产物,提出了四种可能的降解途径,包括羟化、甲酰化、脱氢和脱氯。本研究表明,在基于 PAA 的 AOPs 中,用于控制溶液 pH 的 PBS 应谨慎使用。

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