近年来，基于零价铁的化学还原技术因其高效性逐渐被应用于受污染地下水的原位修复。但是，该技术在实际应用中仍面临一些亟待解决的问题。零价铁作为一种高活性的电子供体，除了和目标污染物反应外，还可以与地下水中其他的氧化性物质（如O2、H+或NO3-等）反应。这些反应所造成的零价铁腐蚀，不仅会降低修复效率还会增加地下水修复成本。此外，同类或多类污染物间也存在对零价铁所释放电子的相互竞争，从而影响各自的去除效率。本文综述了基于零价铁的地下水修复体系中的电子传递过程和氧化物间的电子竞争机制，从零价铁的腐蚀和电子传递、零价铁电子选择性量化指标的提出和量化方法、地下水体中多种共存氧化物间电子竞争作用、电子效率的影响因素以及强化措施等方面进行详细介绍。最后，对该技术今后发展方向作出了展望，以期为其今后实际的地下水修复应用提供参考。
In recent years, the zero-valent iron(ZVI)-based chemical reduction technology has been applied for the in-situ groundwater remediation because of its high efficiency and low cost. However, the technology still faces up some bottleneck restrictions in engineering applications considering the complex groundwater constituents. ZVI, as a highly reactive electron donor, not only reacts with the target contaminants, but also reacts with other co-existing oxidants(O2, H+, NO3-, etc.) in the groundwater, which would negatively impact the remediation efficiency and increase the cost of remediation. In addition, electron competition usually occurs among the contaminants of the same or different categories, consequently resulting in a lower removal efficiency in a multi-solute system than in a single-solute system. Therefore, in this paper, the electron transfer process and the electron competition mechanism among different oxides in ZVI-based groundwater remediation systems are reviewed, including ZVI corrosion and electron transfer, the concept of ZVI reduction selectivity and its quantification methods, the electron competition among various coexisting oxides in groundwater, and the influence factors and enhancement methods of electron efficiency. Finally, the future development direction of the technology is forecast, so as to provide reference for future engineering application of in situ chemical remediation of groundwater.
Contents
1 Introduction
2 Zero-valent iron corrosion and electron-transfer process
2.1 Zero-valent iron corrosion
2.2 Effects of corrosion on the electron-transfer process
3 “Electron selectivity” and “electron efficiency” of ZVI
3.1 Conceptulization and quantification of electron selectivity
3.2 Calculation of “electron efficiency”
4 Electron competition of coexisting oxides
4.1 DO
4.2 H2O or H+
4.3 NO3-
4.4 Heavy metals
4.5 Organic pollutants
5 Influence factors for “electron efficiency”
5.1 The relative proportions of the reducing agent and the oxidant
5.2 pH
5.3 Other factors
6 Technical methods to improve the “electron efficiency”
6.1 “Sulfidation”
6.2 “Magnetization” or “pre-magnetization”
6.3 Zero-valent iron/Fe(Ⅱ)
7 Conclusion and outlook
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