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高锰酸盐氧化人工甜味剂乙酰磺胺酸钾:反应动力学、转化产物与途径及生态毒性。

Oxidative transformation of artificial sweetener acesulfame by permanganate: Reaction kinetics, transformation products and pathways, and ecotoxicity.

机构信息

State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha, 410082, PR China.

College of Finance and Statistics, Hunan University, Changsha, 410082, PR China.

出版信息

J Hazard Mater. 2017 May 15;330:52-60. doi: 10.1016/j.jhazmat.2017.02.012. Epub 2017 Feb 9.

DOI:10.1016/j.jhazmat.2017.02.012
PMID:28208093
Abstract

Acesulfame has attracted much attention due to its wide application, environmental persistence and potential safety risk of transformation products (TPs). Little information is known on acesulfame transformation in the presence of oxidants/disinfectants. The acesulfame oxidation by permanganate (Mn(VII)) in water under environmentally relevant conditions was systematically evaluated. The pH of water showed negligible influence in acesulfame oxidation. Inorganic ligand (pyrophosphate) exhibited insignificant effect whereas organic ligands (oxalate, ethylene diamine tetraacetic acid, and humic acid) exerted obvious suppression on acesulfame oxidation. Natural organic matter in real water had important influence in acesulfame oxidation by Mn(VII). Acesulfame transformation pathways were initiated by the attack of Mn(VII) on double bond of ring via [3+2] addition electrocyclic reaction and rich electron of N moiety through electrophilic reaction, followed by oxidation and hydrolysis reactions to produce TPs. Among them, five TPs were for the first time identified. The ecotoxicity tests uncover higher toxicity of the TPs than acesulfame itself. The study on oxidative transformation of acesulfame by Mn(VII) would illumine comprehensive evaluation of this emerging contaminant. Water treatment plants need to consider cautiously to protect the safety of downstream system when using Mn(VII) to dispose the water resource containing acesulfame or other artificial sweeteners.

摘要

乙酰磺胺酸钾由于其广泛的应用、环境持久性以及其转化产物(TPs)的潜在安全风险而备受关注。关于氧化剂/消毒剂存在下乙酰磺胺酸钾的转化,人们知之甚少。本文系统评估了环境相关条件下过锰酸盐(Mn(VII))对乙酰磺胺酸钾的氧化作用。水的 pH 值对乙酰磺胺酸钾的氧化几乎没有影响。无机配体(焦磷酸根)影响甚微,而有机配体(草酸盐、乙二胺四乙酸和腐殖酸)则明显抑制了乙酰磺胺酸钾的氧化。天然有机物在 Mn(VII)氧化乙酰磺胺酸钾中具有重要影响。乙酰磺胺酸钾的转化途径是通过[3+2]加成电环反应攻击环上的双键和 N 部分的富电子,随后通过氧化和水解反应产生 TPs。其中,有 5 种 TPs 是首次被鉴定出来的。毒性测试表明 TPs 的毒性比乙酰磺胺酸钾本身更高。本研究阐明了 Mn(VII)对乙酰磺胺酸钾的氧化转化机制,为全面评价这种新兴污染物提供了依据。水处理厂在使用 Mn(VII)处理含有乙酰磺胺酸钾或其他人工甜味剂的水资源时,需要谨慎考虑以保护下游系统的安全。

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