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通过甲酸与紫外线联合应用作为一种高级还原工艺降解麦草畏——一种持久性除草剂。

Degradation of dicamba - A persistent herbicide - By combined application of formic acid and UV as an advanced reduction process.

作者信息

Askarniya Zahra, Cichocki Łukasz, Makowiec Sławomir, Wang Chongqing, Boczkaj Grzegorz

机构信息

Department of Sanitary Engineering, Faculty of Civil and Environmental Engineering, Gdansk University of Technology, G. Narutowicza St. 11/12, Gdansk 80 - 233, Poland.

Department of Organic Chemistry, Faculty of Chemistry, Gdansk University of Technology, G. Narutowicza St. 11/12, Gdansk 80 - 233, Poland.

出版信息

J Hazard Mater. 2025 Jul 15;492:137984. doi: 10.1016/j.jhazmat.2025.137984. Epub 2025 Mar 19.

Abstract

The degradation of dicamba as a persistent herbicide was studied with the combined application of UV and formic acid (FA) as a novel advanced reduction process (ARP). The effects of key parameters of FA concentration, dissolved organic matter, and inorganic anions were studied. A 97 % degradation and 94 % dechlorination of dicamba were obtained through the combination of UV and FA (UV-FA) at a dicamba concentration of 0.023 mM and FA concentration of 0.123 M. With respect to the dechlorination, at a dicamba concentration of 0.23 mM, FA concentration of 0.123 M, and pH of 2, chloride concentration of 12.4 mg/L and 5.2 mg/L was obtained for ARP (UV-FA) and sole UV in acidic condition, respectively. Scavenging test using Methyl viologen (MV) as a scavenger for reductive radicals including carboxyl anion radicals (CO¯) led to a decrease in the chloride concentration to 1.7 mg/L, revealing the importance of this radical in the dechlorination of dicamba. Inorganic anions (CO¯ and SO¯) had a slightly positive effect on the degradation of dicamba and led to an increase in degradation to 99 %, while they had a negative effect on the dechlorination by 7 % and 30 %, respectively. Due to the turbidity induced by dissolved organic matters (DOM), a moderate decrease in degradation by 39 % and dechlorination by 30 % was observed. The existence of five intermediates identified by GC-MS technique confirmed the proposed mechanism of dicamba degradation via ARP. Reductive degradation of dicamba mainly consists of processes based on CO¯, including single electron transfer process and radical-nucleophilic aromatic substitution (SRN) reactions, demonstrating the capability of this ARP for the effective degradation of dicamba.

摘要

研究了将紫外线与甲酸(FA)联合应用作为一种新型高级还原工艺(ARP)对持久性除草剂麦草畏的降解情况。研究了FA浓度、溶解有机物和无机阴离子等关键参数的影响。在麦草畏浓度为0.023 mM、FA浓度为0.123 M的条件下,通过紫外线与FA联合作用(UV-FA)可实现麦草畏97%的降解率和94%的脱氯率。就脱氯而言,在麦草畏浓度为0.23 mM、FA浓度为0.123 M且pH为2的条件下,酸性条件下ARP(UV-FA)和单独紫外线作用下的氯离子浓度分别为12.4 mg/L和5.2 mg/L。使用甲基紫精(MV)作为包括羧基阴离子自由基(CO¯)在内的还原自由基清除剂的清除试验导致氯离子浓度降至1.7 mg/L,这表明该自由基在麦草畏脱氯过程中的重要性。无机阴离子(CO¯和SO¯)对麦草畏的降解有轻微的促进作用,使降解率提高到99%,而它们分别对脱氯有7%和30%的负面影响。由于溶解有机物(DOM)引起的浊度,观察到降解率适度下降39%,脱氯率下降30%。通过气相色谱-质谱联用(GC-MS)技术鉴定出的五种中间体的存在证实了通过ARP降解麦草畏的 proposed 机制。麦草畏的还原降解主要由基于CO¯的过程组成,包括单电子转移过程和自由基-亲核芳香取代(SRN)反应,证明了这种ARP对麦草畏有效降解的能力。

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