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亚硝酸盐对硫酸根自由基降解卤代酚的影响

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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/LNO2-,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.
Influence of nitrite on the degradation of halogenated phenols in sulfate radical oxidation processes
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 ofNO2 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.

bromophenolchlorophenolsulfate radicalsnitritenitryl halidesnitrated byproducts

桂静婧、刘佳婷、杨培增、陈静、季跃飞、陆隽鹤

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南京农业大学资源与环境科学学院,江苏南京 210095

溴酚 氯酚 硫酸根自由基 亚硝酸盐 硝酰卤 硝基副产物

国家自然科学基金国家自然科学基金江苏省基础研究计划自然科学基金青年基金江苏省双创博士项目

2207607922076080BK20231005JSSCBS20210264

2024

中国环境科学
中国环境科学学会

中国环境科学

CSTPCDCHSSCD北大核心
影响因子:2.174
ISSN:1000-6923
年,卷(期):2024.44(6)
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