Askarniya Zahra, Cichocki Łukasz, Makowiec Sławomir, Wang Chongqing, Boczkaj Grzegorz
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.
J Hazard Mater. 2025 Jul 15;492:137984. doi: 10.1016/j.jhazmat.2025.137984. Epub 2025 Mar 19.
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.
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。