环境工程学报2025，Vol.19Issue(2)：342-353,12.DOI:10.12030/j.cjee.202410039
二氧化氯降解废水中多柔比星的反应动力学与降解机理
Degradation kinetics and mechanism of doxorubicin in wastewater by chlorine dioxide
摘要
Abstract
In recent years,anthracyclines antibiotics including doxorubicin have been widely used in medical treatment and animal husbandry,and their half-life in water is relatively long,which poses a great threat to human health and the environment.Chlorine dioxide(ClO2)has the potential to degrade antibiotics because of its strong oxidation and free of halogenated disinfection byproducts.Therefore,ClO2 was used to degrade Doxorubicin hydrochloride(DOX),and the influencing factors and the reaction kinetics were explored;meanwhile,high performance liquid chromatography-mass spectrometry was used to identify its degradation products;quantum chemical calculations were used to reveal its reactive sites;and the degradation mechanism was illustrated through the combination of experimental results and theoretical calculations.The results showed that the best DOX degradation effect of ClO2 occurred when the concentration of ClO2 was 0.8mg·L-1,the temperature was 25 ℃,and pH was 7.5,and the degradation rate reached 94.07％.DOX degradation by ClO2 conformed to the second-order reaction kinetic model,and the reaction rate constant was 2.41 × 10-2 mmol·L-1·s-1.The activation energy was 25.46kJ·mol-1.DOX was more easily degraded under alkaline conditions than under acidic conditions.The quantum chemical calculation results showed that the C-C single bond of DOX is vulnerable to nucleophilic attack,and the O-H bond is vulnerable to electrophilic attack.O26,O39 and C20 are electrophilic reaction sites.The results of mass spectrometry showed that free radical hydrogen extraction and addition reactions occurred after DOX was oxidized by ClO2,and the reaction degradation products were M+16,M+32,M-157,M-241,and M-396,respectively,which were basically consistent with the calculated results.It is found that there were more toxic intermediate products by analyzing the changes in toxicity during the degradation of DOX.关键词
多柔比星/二氧化氯/降解动力学/反应历程/量子化学计算Key words
doxorubicin/chlorine dioxide/degration kinetics/reaction pathway/quantum chemical calculation分类
资源环境引用本文复制引用
周美萱,吴明松,刘阳,刘天雨,苗玉颖..二氧化氯降解废水中多柔比星的反应动力学与降解机理[J].环境工程学报,2025,19(2):342-353,12.基金项目
安徽省教育厅重大项目(2024AH040184) （2024AH040184）
驻冀高校成果转化项目(241200074A) （241200074A）
