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亚铁活化过硫酸盐氧化2,4-二硝基甲苯过程中氯离子影响的研究:去除效率、反应机理、转化途径及毒性评估

Insights into the impacts of chloride ions on the oxidation of 2,4-dinitrotoluene using ferrous activated persulfate: Removal efficiency, reaction mechanism, transformation pathway, and toxicity assessment.

作者信息

Li Xiaodong, Shen Jialun, Sun Zongquan, Zhang Wenwen, Ma Fujun, Gu Qingbao

机构信息

State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China.

State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, China.

出版信息

Chemosphere. 2023 Mar;317:137887. doi: 10.1016/j.chemosphere.2023.137887. Epub 2023 Jan 16.

Abstract

Persulfate/Fe-based advanced oxidation processes are widely used to treat water contaminated with 2,4-dinitrotoluene (DNT). However, the oxidation of DNT by persulfate/Fe in the presence of the chloride ion (Cl⁻) has not been addressed, and the transformation pathways and toxicities of the intermediate products remain unclear. In this study, the effect of different Cl⁻ concentrations on the oxidation of DNT was investigated by persulfate/Fe. After the addition of 1.0 mM Cl⁻ and 6 h of oxidation, the removal efficiency of DNT increased by 68.5%. Scavenging experiments and an electron spin resonance analysis suggested that Cl⁻ caused hydroxyl radicals to increase in content in the persulfate/Fe system, thus promoting the removal of DNT. Eight intermediate products of DNT were accurately detected using high-resolution mass spectrometry, and the transformation pathways of DNT were proposed, including hydroxylation/oxidation, elimination of the nitro group, and chlorination process. The acute and chronic toxicities of the intermediate products decreased during the oxidation process, but chlorinated by-products posed a higher toxicological risk. This result is vital for the practical application and environmental safety evaluation of persulfate/Fe-based advanced oxidation.

摘要

过硫酸盐/铁基高级氧化工艺被广泛用于处理受2,4-二硝基甲苯(DNT)污染的水。然而,氯离子(Cl⁻)存在下过硫酸盐/铁对DNT的氧化作用尚未得到研究,中间产物的转化途径和毒性仍不清楚。本研究中,研究了不同Cl⁻浓度对过硫酸盐/铁氧化DNT的影响。加入1.0 mM Cl⁻并氧化6小时后,DNT的去除效率提高了68.5%。清除实验和电子自旋共振分析表明,Cl⁻使过硫酸盐/铁体系中羟基自由基含量增加,从而促进了DNT的去除。使用高分辨率质谱准确检测到了DNT的8种中间产物,并提出了DNT的转化途径,包括羟基化/氧化、硝基消除和氯化过程。氧化过程中中间产物的急性和慢性毒性降低,但氯化副产物具有较高的毒理学风险。该结果对于过硫酸盐/铁基高级氧化的实际应用和环境安全评估至关重要。

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