重金属污染土壤修复的Pb2+钝化产物稳定性

doi:10.13278/j.cnki.jjuese.20190062

摘要/Abstract

摘要： 自然状态下土壤中重金属元素是否稳定存在是重金属污染固化修复技术中的核心问题。本文以常见重金属离子Pb²⁺为例，分析土壤中重金属离子与常见离子基团结合的稳定性。将第一性原理应用于Pb的存在形态和稳定性的分析，计算了PbCO₃、PbSO₄、PbCl₂、Pb₃（PO₄）₂、PbAl₂O₄和Pb₃Fe₂（PO₄）₄的自由能、能带和态密度。首先推断Pb²⁺和CO₃^2-、SO₄^2-、Cl^-、PO₄^3-等土壤中常见阴离子的结合稳定性，再判断加入金属阳离子Al³⁺和Fe³⁺对体系稳定性的影响。结果表明：铅化合物自由能从高到低趋势为PbCl₂、PbAl₂O₄、PbCO₃、PbSO₄、Pb₃（PO₄）₂、Pb₃Fe₂（PO₄）₄，其相应的结构稳定性顺序从大到小为Pb₃Fe₂（PO₄）₄、Pb₃（PO₄）₂、PbSO₄、PbCO₃、PbAl₂O₄、PbCl₂。通过对能带和态密度的分析，首先确定了SO₄^2-和PO₄^3-的引入能够增强含Pb体系的稳定性，进一步加入金属阳离子Fe³⁺会使体系更稳定。推测SO₄^2-、PO₄^3-为治理Pb²⁺污染合适的官能团，应选择容易释放SO₄^2-、PO₄^3-的物质作为合适的钝化剂。在实际应用中可选择磷酸二氢钠、无水硫酸钠、脱硫石膏等作为钝化剂。

关键词: Pb²⁺, 第一性原理, 自由能, 能带结构, 态密度, 稳定性

Abstract: The heavy metal elements in soil under natural conditions is a core concern in the solidification remediation of heavy metal pollution. Taking the common heavy metal Pb²⁺ as an example, the authors calculated the binding stability of heavy metals with ion groups in soil through applying the first principle to the analysis. The free energy, energy band,and density of states of PbCO₃, PbSO₄, PbCl₂, Pb₃(PO₄)₂, PbAl₂O_4, and Pb₃Fe₂(PO₄)₄ were calculated. The binding stability of Pb²⁺ with anions in soil such as CO₃^2-, SO₄^2-, Cl^- and PO₄^3- was deduced firstly, and then the influence of adding metal cations of Al³⁺ and Fe³⁺on the stability. The results show that the trend of free energy of lead compounds is Pb₃Fe₂(PO₄)₄ < Pb₃(PO₄)₂ < PbSO₄ < PbCO₃ < PbAl₂O₄ < PbCl₂, and the corresponding order of structural stability is PbCl₂ < PbAl₂O₄ < PbCO₃ < PbSO₄ < Pb₃(PO₄)₂ < Pb₃Fe₂(PO₄)₄. Through the analysis of energy band and density of states, it is considered that the introduction of SO₄^2- and PO₄^3- can enhance the stability of the lead-containing system, and further addition of the metal cation Fe³⁺ will make the system more stable. It is suggested that SO₄^2- and PO₄^3- are suitable functional groups for the treatment of Pb²⁺ pollution, and the substances easily to release SO₄^2- and PO₄^3- should be selected as the appropriate passivator.In future work, sodium dihydrogen phosphate,sodium sulfate and desulfurized gypsum can be used as passivators in field experiments.

Key words: Pb²⁺, first principle, free energy, band structure, density of states, stability

中图分类号:

P594

赵玉岩, 姜伟明, 臧利斌, 孙文, 汤肖丹. 重金属污染土壤修复的Pb²⁺钝化产物稳定性[J]. 吉林大学学报(地球科学版), 2020, 50(3): 875-882.

Zhao Yuyan, Jiang Weiming, Zang Libin, Sun Wen, Tang Xiaodan. Stability of Pb²⁺ Passivation Products for Heavy Metal Contaminated Soil Remediation[J]. Journal of Jilin University(Earth Science Edition), 2020, 50(3): 875-882.

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重金属污染土壤修复的Pb²⁺钝化产物稳定性

Stability of Pb²⁺ Passivation Products for Heavy Metal Contaminated Soil Remediation

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