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腐殖酸强化微生物燃料电池对钒污染土壤的修复

Enhanced remediation of vanadium contaminated soil by microbial fuel cells with the addition of humic acid and fulvic acid

  • 摘要: 为探究土壤微生物燃料电池(soil microbial fuel cell,SMFC)中产电性能及其对污染土壤中钒迁移转化效果,设置开路(open circuit,OC)、闭路(closed circuit,CC)、添加胡敏酸(humic acid,HA)或富里酸(fulvic acid,FA)4种处理组,并测定其电化学性能、土壤理化性质以及有机质组分的变化,重点研究了重金属钒在土壤中的迁移转化规律。结果表明:与SMFC-OC相比,SMFC-CC、SMFC-HA和SMFC-FA的电化学性能、钒的阴极富集率增加,其中SMFC-FA组的运行效果最佳,其输出电压稳定在669.32 mV左右,最大功率密度为40.08 mW/m2。SMFC中钒主要在电迁移作用下实现了向阴极迁移,经SMFC修复后,土壤中钒的弱酸提取态逐渐转化为更加稳定的残渣态,其中添加富里酸使残渣态的钒从38%增加到54%。土壤中V5+在微生物和电场的作用下被还原为V4+,迁移至阴极后并富集,富里酸组富集率达到28.17%。此外,富里酸的存在导致电活性细菌数量、有机质和胞外聚合物的浓度增加,更有利于钒的迁移转化。综上,该研究揭示了腐殖酸强化微生物燃料电池的作用机制,为生物电化学技术在钒污染土壤修复中的应用提供了理论依据。

     

    Abstract: With the development and utilization of vanadium and titanium resources, vanadium enters the surrounding soil and groundwater, which affects the ecological environment and poses a risk to human health, so it is important to find an environmentally friendly material for the treatment of vanadium-contaminated soil. Vanadium exists in the environment in divalent, trivalent, tetravalent and pentavalent states, with pentavalent and tetravalent states being the most common in nature, and the toxicity of vanadium depends on the valence state, with higher valence states being more toxic and migratory. Humic acid as a natural organic matter, exhibits a unique mechanism of electron transfer and microbial synergy during vanadium reduction. In order to investigate the power production in soil microbial fuel cell (SMFC) and its effect on vanadium migration and transformation in polluted soil, In this study, vanadium was used as a target pollutant, and Geobacter metallireducens was used as a test strain. Four treatment groups, namely, open circuit (OC), closed circuit (CC), humic acid (HA) or fulvic acid (FA), were set up and their electrochemical performance was determined. The four treatment groups of open circuit (OC), closed circuit (CC), humic acid (HA) or fulvic acid (FA) were added, and the electrochemical properties, soil physicochemical properties, and changes in the organic matter fractions were determined, focusing on the transport and transformation of vanadium heavy metals in the soil. The results showed that the electrochemical performance and the cathodic enrichment rate of vanadium increased in SMFC-CC, SMFC-HA and SMFC-FA compared with SMFC-OC, among which SMFC-FA operated the best, with its output voltage stabilized at about 669.32 mV and the maximum power density of 40.08 mW/m2. Vanadium in SMFC was mainly realized to the cathode under the effect of electromigration. The cathode migration of vanadium in the soil was gradually transformed into a more stable residual state after remediation by SMFC, in which the addition of fulvic acid increased the vanadium in the residual state from 38% to 54%. Comparative analysis of the changes in vanadium concentration in the cathode and anode regions in the SMFC reveals that vanadium is ultimately enriched in the cathode region, and the enrichment rate of vanadium in the cathode region is positively correlated with the electrochemical performance of the SMFC. V5+ in the soil was reduced to V4+ by microorganisms and electric field, migrated behind the cathode and enriched, with the enrichment rate reaching 28.17% in the fulvic acid group.SEM was used to observe the microscopic morphology of the anodic biofilm, FTIR to analyze the changes in the functional groups of soil humic acids, and three-dimensional fluorescence spectroscopy to resolve the electron shuttling substances and extracellular polymers in SMFC.Comparing the strengthening effects of fulvic acid and humic acid, the fulvic acid system demonstrated superior restorative potential. In addition, the presence of fulvic acid led to an increase in the number of electroactive bacteria, the concentration of organic matter and extracellular polymers, which was more favorable for vanadium migration and transformation. In conclusion, this study revealed the mechanism of humic acid-enhanced microbial fuel cells and provided a theoretical basis for the application of bioelectrochemical technology in the remediation of vanadium-contaminated soil.

     

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