Cheng Dong, Ding Haoran, Tan Yuansen, Yang Dezhi, Pan Ying, Liao Wenjuan, He Feng
College of Environment, Zhejiang University of Technology, Hangzhou 310014, China.
College of Resources, Hunan Agricultural University, Changsha 410128, China.
J Hazard Mater. 2023 Oct 5;459:132260. doi: 10.1016/j.jhazmat.2023.132260. Epub 2023 Aug 9.
Oxidizing potential of FeS for organic contaminants degradation due to hydroxyl radicals (•OH) production has been recently documented, but the oxidizing efficiency was limited. Here, we revealed that low-molecular-weight organic acids (LMWOAs) can immensely enhance phenol degradation during FeS oxygenation due to increased utilization efficiency of FeS electron for •OH production. Upon oxygenation of 0.5 g/L FeS, phenol degradation boosted from 7.1% without LMWOAs to 91.5%, 84.6% and 95.0% with the addition of 1 mM oxalate, citrate and EDTA, respectively. Electron utilization efficiency of Fe(II) for •OH production dramatically rose from 0.3% with FeS alone to respective 2.0%, 2.5% and 2.7% in the LMWOAs systems. An increase in oxalate concentrations benefited •OH formation and phenol degradation. Coexisting oxalate led to an additional •OH production pathway from Fe(II)-oxalate oxidation, which expanded the O reduction to HO from a two- to one-electron transfer process. Meanwhile, electron transfer from FeS to dissolved Fe(III)-oxalate promoted the redox cycling of Fe(III)/Fe(II), thus supplying the Fe(II) oxidation for •OH production. Moreover, the presence of oxalate decreased the crystallinity and particles size of lepidocrocite generated from FeS oxidation. Consequently, this study shed lights on the LMWOAs-enhanced contaminant degradation in either natural or engineered FeS oxidation systems.
最近有文献记载了FeS因产生羟基自由基(•OH)而对有机污染物的氧化潜力,但氧化效率有限。在此,我们发现低分子量有机酸(LMWOAs)可极大地增强FeS氧化过程中苯酚的降解,这是由于FeS电子用于•OH生成的利用效率提高。在0.5 g/L FeS氧化过程中,添加1 mM草酸盐、柠檬酸盐和EDTA后,苯酚降解率分别从无LMWOAs时的7.1%提高到91.5%、84.6%和95.0%。Fe(II)用于•OH生成的电子利用效率从单独使用FeS时的0.3%大幅提高到LMWOAs体系中的2.0%、2.5%和2.7%。草酸盐浓度的增加有利于•OH的形成和苯酚的降解。共存的草酸盐导致了Fe(II)-草酸盐氧化产生额外的•OH生成途径,将O还原为HO的过程从两电子转移过程扩展为单电子转移过程。同时,电子从FeS转移到溶解的Fe(III)-草酸盐促进了Fe(III)/Fe(II)的氧化还原循环,从而为•OH生成提供了Fe(II)氧化。此外,草酸盐的存在降低了FeS氧化生成的纤铁矿的结晶度和颗粒尺寸。因此,本研究揭示了LMWOAs在天然或工程FeS氧化系统中增强污染物降解的作用。