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亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成

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季跃飞, 赵旭蕾, 张藤, 陆隽鹤. 亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成[J]. 环境化学, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
引用本文: 季跃飞, 赵旭蕾, 张藤, 陆隽鹤. 亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成[J]. 环境化学, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
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JI Yuefei, ZHAO Xulei, ZHANG Teng, LU Junhe. Transformation of 4-chlorophenol and formation of chloronitrophenol in a sulfate radical-based advanced oxidation process in the presence of nitrite[J]. Environmental Chemistry, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
Citation: JI Yuefei, ZHAO Xulei, ZHANG Teng, LU Junhe. Transformation of 4-chlorophenol and formation of chloronitrophenol in a sulfate radical-based advanced oxidation process in the presence of nitrite[J]. Environmental Chemistry, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
shu

亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成

  • 南京农业大学, 资源与环境科学学院, 南京, 210095

    • 通讯作者: 陆隽鹤, E-mail: jhlu@njau.edu.cn
  • 基金项目:

    国家自然科学基金（21607077）资助.

Transformation of 4-chlorophenol and formation of chloronitrophenol in a sulfate radical-based advanced oxidation process in the presence of nitrite

  • College of Resources and Environmental Sciences, Nanjing Agricultural University, Nanjing, 210095, China

    • Corresponding author: LU Junhe, jhlu@njau.edu.cn
  • Fund Project: Supported by the National Natural Science Foundation of China (21607077).

  • 摘要: 硫酸根自由基（SO4·-）高级氧化工艺（SR-AOPs）被广泛应用于土壤和地下水污染修复，然而其使用过程中生成的有毒有害副产物尚未引起重视.本研究以热活化过硫酸盐（PS）为反应体系，考察亚硝酸盐（NO2-）对4-氯酚（4CP）转化和产物生成的影响.色谱-质谱联用分析表明， SO4·-可介导亚硝态氮掺入4CP分子结构，生成4-氯-2-硝基酚（4C2NP）.4C2NP的生成是4CP酚氧自由基（ClPhO·）与二氧化氮自由基（NO2·）相互耦合的结果.在50 μmol·L-1 4CP、 2 mmol·L-1 PS、溶液pH 7.0、加热温度50 ℃、NO2-浓度50—400 μmol·L-1条件下，4C2NP产率介于57.9%—91.8%之间.在中性pH条件下，4C2NP在热活化PS体系中可发生进一步转化.增加NO2-浓度稍微抑制了4CP的转化，却显著提高了4C2NP的产率.Suwannee河富里酸（SRFA）的存在缓减了4CP的转化，但4CP转化生成4C2NP仍然是其消亡的主要途径.结果说明，在NO2-存在下，采用SR-AOPs处理氯酚可生成具有"三致"效应的硝基氯酚，必须引起足够重视.
    Abstract: Sulfate radical (SO4·-)-based advanced oxidation processes (SR-AOPs) are widely used for remediation of contaminated groundwater and soil. However, the potential formation of hazardous by-products has received little attention. This study investigated the influences of nitrite (NO2-) on the transformation of 4-chlorophenol (4CP) and the formation of by-products in the thermally activated persulfate (PS) oxidation process. Analysis of liquid chromatography-mass spectrometry showed that NO2- could induce the incorporation of nitrite nitrogen into 4CP, leading to the formation of 4-chloro-2-nitrophenol (4C2NP). The formation of 4C2NP was a result of the combination of 4CP phenoxyl radical and nitrogen dioxide radical (NO2·). Under the reaction condition of 50 μmol·L-1 4CP, 2 mmol·L-1 PS, pH 7.0, and 50 ℃, the yield of 4C2NP ranged from 57.9% to 91.8% with NO2- concentration of 50 to 400 μmol·L-1. At neutral pH condition, 4C2NP was subject to further transformation in the thermally activated PS system. Increasing NO2- concentration inhibited the transformation of 4CP slightly but enhanced the formation of 4C2NP significantly. The presence of Suwannee River fulvic acid (SRFA) retarded the transformation of 4CP. However, nitration to 4C2NP was still a predominant pathway. These results reveal that SO4·--based advanced oxidation of chlorophenols in the presence of NO2- can produce toxic chloronitrophenols, which should receive adequate attention.
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  • 收稿日期:  2019-04-01
季跃飞, 赵旭蕾, 张藤, 陆隽鹤. 亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成[J]. 环境化学, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
引用本文: 季跃飞, 赵旭蕾, 张藤, 陆隽鹤. 亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成[J]. 环境化学, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
shu
JI Yuefei, ZHAO Xulei, ZHANG Teng, LU Junhe. Transformation of 4-chlorophenol and formation of chloronitrophenol in a sulfate radical-based advanced oxidation process in the presence of nitrite[J]. Environmental Chemistry, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
Citation: JI Yuefei, ZHAO Xulei, ZHANG Teng, LU Junhe. Transformation of 4-chlorophenol and formation of chloronitrophenol in a sulfate radical-based advanced oxidation process in the presence of nitrite[J]. Environmental Chemistry, 2020, (4): 852-858. doi: 10.7524/j.issn.0254-6108.2019040103
shu

亚硝酸盐存在下4-氯酚在硫酸根自由基高级氧化工艺中的转化及硝基氯酚的生成

    通讯作者: 陆隽鹤, E-mail: jhlu@njau.edu.cn
  • 南京农业大学, 资源与环境科学学院, 南京, 210095
  • 收稿日期:  2019-04-01
基金项目:

国家自然科学基金（21607077）资助.

摘要: 硫酸根自由基（SO4·-）高级氧化工艺（SR-AOPs）被广泛应用于土壤和地下水污染修复，然而其使用过程中生成的有毒有害副产物尚未引起重视.本研究以热活化过硫酸盐（PS）为反应体系，考察亚硝酸盐（NO2-）对4-氯酚（4CP）转化和产物生成的影响.色谱-质谱联用分析表明， SO4·-可介导亚硝态氮掺入4CP分子结构，生成4-氯-2-硝基酚（4C2NP）.4C2NP的生成是4CP酚氧自由基（ClPhO·）与二氧化氮自由基（NO2·）相互耦合的结果.在50 μmol·L-1 4CP、 2 mmol·L-1 PS、溶液pH 7.0、加热温度50 ℃、NO2-浓度50—400 μmol·L-1条件下，4C2NP产率介于57.9%—91.8%之间.在中性pH条件下，4C2NP在热活化PS体系中可发生进一步转化.增加NO2-浓度稍微抑制了4CP的转化，却显著提高了4C2NP的产率.Suwannee河富里酸（SRFA）的存在缓减了4CP的转化，但4CP转化生成4C2NP仍然是其消亡的主要途径.结果说明，在NO2-存在下，采用SR-AOPs处理氯酚可生成具有"三致"效应的硝基氯酚，必须引起足够重视.

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