亚硝酸盐对硫酸根自由基降解卤代酚的影响

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摘要系统研究了亚硝酸盐(NO₂-)对硫酸根自由基(SO₄^•–)降解溴酚和氯酚的影响.结果表明,NO₂-的加入明显促进了溴酚的降解,而氯酚的降解仅受到轻微促进;此外,两者都转化生成了有毒硝基产物.研究发现,卤代酚在SO₄^•–氧化过程中发生脱卤反应,脱下来的卤离子被SO₄^•–氧化为卤自由基和自由卤.其随后和中间产物甚至母体反应,生成卤代副产物,如卤仿和卤乙酸.若反应过程中存在NO₂-,首先,原位生成的活性卤物质能够被NO₂-迅速捕获,生成强氧化性的硝酰卤.硝酰卤进攻卤代酚,导致其加速降解并生成硝基副产物.其次,NO₂-被SO₄^•–氧化生成二氧化氮自由基(NO₂^·),其随后与卤代酚转化生成的酚氧自由基中间体结合,同样产生大量硝基卤代产物.数据显示,硝基溴酚的种类更多且产量更高.当加入200μmol/L NO₂-,溶液中硝基溴酚和硝基氯酚的总生成量最高分别可至9.2和5.7μmol/L.这是因为在SO₄^•–氧化过程中,溴酚较氯酚更容易发生脱卤反应,因此NO₂-对溴酚转化行为的影响更显著.研究揭示了SO₄^•–氧化技术应用于地下环境中降解卤代污染物时的潜在风险,并对该过程中氮素和卤素的相互转化提供了新的见解.

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	桂静婧
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	陈静
	季跃飞
	陆隽鹤

关键词 ：溴酚, 氯酚, 硫酸根自由基, 亚硝酸盐, 硝酰卤, 硝基副产物

Abstract：The influence of nitrite (NO₂-) on the degradation of bromophenol and chlorophenol by sulfate radical (SO₄^•–) oxidation was systematically investigated in this work. Results showed that the presence of NO₂- accelerated the degradation of bromophenol, while posed a weak effect on the degradation of chlorophenol. Meanwhile, NO₂- led to a series of toxic nitrated byproducts. Upon SO₄^•– oxidation, halophenols underwent dehalogenation and the released halides can be further oxidized by SO₄^•– to form reactive halogen species, which rapidly react with some intermediates and the parent compounds to form halogenated byproducts, such as haloform and haloacetic acid. Once NO₂- was co-present, these reactive halogen species can be scavenged by NO₂- to form a strong oxidizing agent, nitryl halide. Then nitryl halide reacts with the parent halophenol, promoting their degradation and resulting in the formation of nitrated byproducts. Besides, NO₂- can be oxidized to nitrogen dioxide radicals (NO₂^·) by SO₄^•–, which further couple with phenoxy radicals generated from the oxidation of halophenols by SO₄^•–, yielding nitrated byproducts as well. Note that, the formation of nitrated byproducts from bromophenol (9.2 μmol/L) was significantly higher than those generated from chlorophenol (5.7μmol/L) with 200 μmol/L NO₂- present. In SO₄^•– oxidation process, bromophenol is more prone to dehalogenation than chlorophenol. Therefore, the influence of NO₂- on the transformation of bromophenol was more drastic than that of chlorophenol by SO₄^•–. These findings reveal potential risks of the application of SO₄^•– oxidation technologies for the remediation of halogenated contaminants in the subsurface environment, and provide new insights into the interaction of nitrogen and halogen in SO₄^•– oxidation processes.

Key words： bromophenol chlorophenol sulfate radicals nitrite nitryl halides nitrated byproducts

收稿日期: 2023-11-19

PACS:

X703.5

基金资助:国家自然科学基金资助项目(22076079,22076080);江苏省基础研究计划自然科学基金青年基金项目(BK20231005);江苏省双创博士项目(JSSCBS20210264)

通讯作者: 杨培增,讲师,peizeng@njau.edu.cn E-mail: peizeng@njau.edu.cn

作者简介: 桂静婧(2000-),女,新疆沙湾人,南京农业大学硕士研究生,主要研究方向为水环境化学.发表论文1篇.guijingjing0906@163.com.

引用本文:

桂静婧, 刘佳婷, 杨培增, 陈静, 季跃飞, 陆隽鹤. 亚硝酸盐对硫酸根自由基降解卤代酚的影响[J]. 中国环境科学, 2024, 44(6): 3395-3407. GUI Jing-jing, LIU Jia-ting, YANG Pei-zeng, CHEN Jing, JI Yue-fei, LU Jun-he. Influence of nitrite on the degradation of halogenated phenols in sulfate radical oxidation processes. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(6): 3395-3407.

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