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电化学氧化法在水溶液中使用混合金属氧化物电极对氟苯尼考的研究:操作因素、反应副产物和毒性评价。

Electrochemical oxidation of Florfenicol in aqueous solution with mixed metal oxide electrode: Operational factors, reaction by-products and toxicity evaluation.

机构信息

Environmental and Water Resources Division, Department of Civil Engineering, Indian Institute of Technology Madras, Chennai-600036, Tamil Nadu, India.

Department of Environmental Science, Central University of Kerala, Kasaragod, Kerala, India.

出版信息

Chemosphere. 2024 Aug;362:142665. doi: 10.1016/j.chemosphere.2024.142665. Epub 2024 Jun 19.

Abstract

Veterinary antibiotics have become an emerging pollutant in water and wastewater sources due to excess usage, toxicity and resistance to traditional water and wastewater treatment. The present study explored the degradation of a model antibiotic- Florfenicol (FF) using electrochemical oxidation (EO) with Ti-RuO/IrO anode. The anode material was characterized using SEM-EDS studies expressing stable structure and optimal interaction of the neighboring metal oxides with each other. The EDS results showed the presence of Ru, Ir, Ti, O and C elements with 6.44%, 2.57%, 9.61%, 52.74% and 28.64% atomic weight percentages, respectively. Optimization studies revealed pH 5, 30 mA cm current density and 0.05 M NaSO for 5 mg L FF achieved 90% TOC removal within 360 min treatment time. The degradation followed pseudo-first order kinetics. LC-Q-TOF-MS studies revealed six predominant byproducts illustrating hydroxylation, deflourination, and dechlorination to be the major degradation mechanisms during the electrochemical oxidation of FF. Ion chromatography studies revealed an increase in Cl, F and NO ions as treatment time progressed with Cl decreasing after the initial phase of the treatment. Toxicity studies using Zebrafish (Danio rerio) embryo showed the treated sample to be toxic inducing developmental disorders such as pericardial edema, yolk sac edema, spinal curvature and tail malformation at 96 h post fertilization (hpf). Compared to control, delayed hatching and coagulation were observed in treated embryos. Overall, this study sets the stage for understanding the effect of mixed metal oxide (MMO) anodes on the degradation of veterinary antibiotic-polluted water and wastewater sources using electrochemical oxidation.

摘要

兽用抗生素由于过量使用、毒性和对传统水和废水处理的耐药性,已成为水和废水中的一种新兴污染物。本研究探索了使用 Ti-RuO/IrO 阳极的电化学氧化 (EO) 对模型抗生素-氟苯尼考 (FF) 的降解。通过 SEM-EDS 研究对阳极材料进行了表征,结果表明该结构稳定,相邻金属氧化物之间相互作用良好。EDS 结果表明,存在 Ru、Ir、Ti、O 和 C 元素,其原子重量百分比分别为 6.44%、2.57%、9.61%、52.74%和 28.64%。优化研究表明,在 pH 5、电流密度 30 mA·cm-2 和 0.05 M Na2SO4 条件下,对 5 mg·L-1 的 FF 处理 360 min 可达到 90%的 TOC 去除率。降解过程遵循准一级动力学。LC-Q-TOF-MS 研究表明,在 FF 的电化学氧化过程中,主要降解机制为羟化、脱氟和脱氯,共产生 6 种主要的中间产物。离子色谱研究表明,随着处理时间的延长,Cl、F 和 NO 离子的含量增加,而在处理初始阶段后 Cl 离子的含量降低。使用斑马鱼(Danio rerio)胚胎进行的毒性研究表明,处理后的样品具有毒性,在受精后 96 小时(hpf)时会引起心脏水肿、卵黄囊水肿、脊柱弯曲和尾巴畸形等发育障碍。与对照组相比,在处理后的胚胎中观察到孵化延迟和凝结。总的来说,这项研究为理解混合金属氧化物 (MMO) 阳极对使用电化学氧化处理兽用抗生素污染水和废水源的影响奠定了基础。

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