微量铜离子联合碳酸氢盐类芬顿体系降解水中双酚A

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摘要基于铜离子（Cu²⁺）的类芬顿体系通常需要较高的Cu²⁺剂量，可能导致二次污染，为解决这一问题，构建了微量Cu²⁺（2.5 μmol/L）联合碳酸氢盐活化过氧化氢（Cu²⁺/H₂O₂/HCO₃^-）体系用于水中双酚A （BPA）的高效降解.结果表明：在一定范围内，Cu²⁺/H₂O₂/HCO₃^-体系对BPA的降解效果随Cu²⁺投加量的升高而上升，随H₂O₂和HCO₃^-投加量的升高呈先上升再降低的趋势.在溶液初始pH值5.06~11.02范围内，BPA均可得到有效去除，且升高反应温度可促进BPA的降解.Cl^-、HPO₄^2-、腐殖酸会抑制BPA降解，而NO₃^-、SO₄^2-的影响则可以忽略不计.活性物种猝灭和捕获实验表明，单线态氧和Cu³⁺是BPA降解过程的主要活性物种.CuCO₃（aq）可能是H₂O₂活化生成的活性氧化物种与Cu³⁺的主要络合物.同时，Cu²⁺/H₂O₂/HCO₃^-对天然水体基质中的BPA也有较好的去除效果.另外根据5种鉴定的中间体，提出了Cu²⁺/H₂O₂/HCO₃^-体系中BPA的可能降解途径.

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	辛丽红
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	张艺民
	袁玉龙
	丁明军
	王鹏

关键词 ：双酚A, 微量铜离子, 碳酸氢盐, 过氧化氢, 降解

Abstract：Higher Cu²⁺ dosage is typically needed for Fenton-like systems based on copper ions (Cu²⁺), which could result in secondary pollution. In the current study, an effective system for degrading bisphenol A(BPA) was built using bicarbonate-activated hydrogen peroxide and trace copper ions (Cu²⁺/H₂O₂/HCO₃^-). According to the findings, increasing the Cu²⁺ dosage boosted the removal efficiency of BPA, while increasing the H₂O₂ or HCO₃^- dosage caused the trend to grow initially before declining. BPA can be effectively removed within the range of the initial pH value of solution 5.06~11.02, and the degradation efficiency was improved with increased temperature. The presence of Cl^-、HPO₄^2- and humic acid (HA) were found to delayed the elimination of BPA, while other anions like NO₃^- and SO₄^2- had no obvious effects. Quenching and trapping experiments showed that the identified single oxygen and Cu³⁺ were the predominant reactive species responsible for BPA degradation. CuCO₃(aq) was the major complex with a high reactivity for H₂O₂ activation to form reactive oxygen species (ROS) and Cu³⁺. At the same time, there is a good removal effect of BPA in the natural water matrix of the Cu²⁺/H₂O₂/HCO₃^- system. In addition, the mechanism of possible degradation of BPA in Cu²⁺/H₂O₂/HCO₃^- has been proposed from the five identified intermediates.

Key words： bisphenol A trace copper bicarbonate hydrogen peroxide degradation

收稿日期: 2022-07-07

PACS:

X703.1

基金资助:国家自然科学基金项目（42067034，42067058）；江西省主要学科学术和技术带头人培养计划（20212BCJL23058）；自然部生态地球化学重点实验室开放基金（ZSDHJJ202004）

通讯作者: 聂明华,副教授,mhnie@jxnu.edu.cn E-mail: mhnie@jxnu.edu.cn

作者简介: 辛丽红(1999-),女,江西宜春人,江西师范大学硕士研究生,主要研究方向为环境污染与防治.

引用本文:

辛丽红, 晏彩霞, 聂明华, 张艺民, 袁玉龙, 丁明军, 王鹏. 微量铜离子联合碳酸氢盐类芬顿体系降解水中双酚A[J]. 中国环境科学, 2023, 43(3): 1186-1196. XIN Li-hong, YAN Cai-xia, NIE Ming-hua, ZHANG Yi-min, YUAN Yu-long, DING Ming-jun, WANG Peng. Degradation of bisphenol A by Fenton-like system using trace copper ions combined with bicarbonate in water. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(3): 1186-1196.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2023/V43/I3/1186

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