小分子有机酸协同菱铁矿氧化固定As(III)的机制研究

尹正; 高宇阳; 于雪辉; 秦文秀; 司友斌

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (8) : 4470-4481.

土壤污染与控制

小分子有机酸协同菱铁矿氧化固定As(III)的机制研究

尹正, 高宇阳, 于雪辉, 秦文秀, 司友斌

作者信息 +

Mechanistic insights into the oxidative fixation of As(III) by siderite in synergy with low molecular weight organic acids

YIN Zheng, GAO Yu-yang, YU Xue-hui, QIN Wen-xiu, SI You-bin

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摘要

聚焦于小分子有机酸(草酸(OA)、柠檬酸(CA)、没食子酸(GA))协同Fe(II)矿物产生活性氧(ROS)氧化固定As(III).采用菱铁矿(FeCO₃)为受试矿物,探讨了吸附态和共沉淀态FeCO₃-小分子有机酸复合物对As(III)氧化特性,并分析了氧化过程中产生羟基自由基(•OH)和Fe的形态变化,以及自由基淬灭剂和C/Fe摩尔比对As(III)氧化和As(T)固定的影响.结果表明,外源添加0.05~0.5mmol/L小分子有机酸会促进菱铁矿对As(III)的氧化,其中GA>CA>OA,GA存在下As(III)去除率最高为80%;对于吸附态和共沉淀态复合物,C/Fe摩尔比增大,氧化能力增强,其中共沉淀态FeCO₃-CA对As(III)的氧化率最高可达到92.1%.自由基淬灭剂甲醇和NBT显著抑制As(III)氧化,证明氧化As(III)的主要活性物质为O₂^•−和•OH.不同小分子有机酸与As(III)竞争•OH能力不同,其中共沉淀态FeCO₃-GA复合物中OC矿化率最高为72.2%,•OH氧化是氧化过程中OC损失的主要原因.SEM、XRD表明菱铁矿反应后向赤铁矿转变.本研究不仅揭示了小分子有机酸与含铁矿物在砷氧化过程中的协同作用机制,而且为砷污染的环境治理提供了新的视角和策略.

Abstract

The present study focused on the oxidative fixation of As(III) by Fe(II)-containing minerals in coordination with low molecular weight organic acids (LMWOA) (such as oxalic acid (OA), citric acid (CA), gallic acid (GA)) to generate reactive oxygen species (ROS). Siderite (FeCO₃) was utilized as the test mineral to investigate the capacity of FeCO₃-LMWOA complexes in adsorbed and co-precipitated states for As(III) oxidation, and to analyze the generation of hydroxyl radicals (•OH) and the morphological changes of Fe during the oxidation process, as well as the effects of radical quenchers and C/Fe molar ratio on As(III) oxidation and As(T) immobilization. The results demonstrated that adding 0.05~0.5mmol/L LMWOA enhanced the oxidation of As(III) by siderite, with the order of GA>CA>OA, and the removal rate of As(III) in the presence of GA was up to 80%. For the adsorbed and co-precipitated complexes, the oxidative capacity was enhanced by increasing C/Fe, and the co-precipitated FeCO₃-CA complex exhibited the highest removal efficiency of As(III), reaching 92.1%. The free radical quencher methanol and NBT exhibited obvious inhibition on As(III) oxidation, which proved that the main active substances for oxidizing As(III) were O₂^•− and •OH. The ability of different LMWOA to compete with As(III) for •OH was different, among which the co-precipitated FeCO₃-GA complex had the highest OC mineralization rate of 72.2%, and the main reason for the OC loss was the oxidation by •OH. SEM and XRD analyses showed that siderite was transformed to hematite after reaction. This study not only reveals the synergistic mechanism between Fe(II)-containing minerals and LMWOA in As(III) oxidation, but also provides new perspectives and strategies for the environmental management of arsenic pollution.

导出引用

尹正, 高宇阳, 于雪辉, 秦文秀, 司友斌. 小分子有机酸协同菱铁矿氧化固定As(III)的机制研究[J]. 中国环境科学. 2025, 45(8): 4470-4481

YIN Zheng, GAO Yu-yang, YU Xue-hui, QIN Wen-xiu, SI You-bin. Mechanistic insights into the oxidative fixation of As(III) by siderite in synergy with low molecular weight organic acids[J]. China Environmental Science. 2025, 45(8): 4470-4481

中图分类号： X53

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