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摘要:
随着重金属污染的日益严重，固定化土壤中的重金属成为近年来学者们研究的热点，矿物材料在其中拥有不可替代的地位。本文针对目前现存的重金属土壤污染问题，概括蒙脱石、海泡石、沸石、高岭土、凹凸棒等黏土矿物及磷酸盐矿物、纳米矿物材料等几种矿物材料在重金属污染土壤稳定化修复领域的应用和反应机理。黏土矿物的稳定化能力与矿物结构有关，矿物结构决定其离子交换能力，离子交换能力强的矿物稳定化效果更为突出，同时黏土矿物亦能改变土壤的pH值等理化性质，使土壤内重金属活性降低。磷酸盐矿物的稳定化能力与其本身的溶解性呈正相关，反应机理主要为溶解-沉淀、表面吸附、离子交换、诱导吸附几种形式。纳米矿物材料在保留原材料性质的基础上，因其粒度为纳米级也展现出一些其他特性。今后可在材料回收循环利用、矿物改性方法优化、提高重金属稳定化效果和减少稳定化周期等方向进行深入研究，以期为稳定化修复土壤中重金属的研究工作提供参考意见。
Abstract:With the increasingly serious pollution of heavy metals, the heavy metals in immobilized soil have become the focus of research in recent years, and mineral materials play an irreplaceable role in it. In this paper, the application and reaction mechanism of montmorillonite, sepiolite, zeolite, kaolin, attapulgite and other clay minerals as well as phosphate minerals and nano-mineral materials in the stabilization and remediation of heavy metal contaminated soil are summarized. The stabilization ability of clay minerals is related to mineral structure, which determines its ion-exchange ability. The stabilization effect of minerals with strong ion-exchange ability is more prominent. At the same time, clay minerals can also change the physical and chemical properties of soil, such as pH value, and reduce the activity of heavy metals in soil.The stabilization ability of phosphate minerals is positively correlated with its solubility, and the reaction mechanisms are mainly solution-precipitation, surface adsorption, ion exchange and induced adsorption. On the basis of retaining the properties of raw materials, nano-mineral materials also show some other characteristics due to their nano-size. In the future, further research can be conducted in the direction of material recovery and recycling, optimization of mineral modification methods, improvement of the stabilization effect of heavy metals and reduction of the stabilization period, in order to provide references for the research work of stabilization and remediation of heavy metals in soil.
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Key words:
- mineral materials /
- heavy metal pollution /
- clay minerals /
- phosphate mineral
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表 1 重金属污染土壤修复常用硅酸盐黏土矿物特点
Table 1. Characteristics of silicate clay minerals commonly used in heavy metal contaminated soil remediation
名称 化学成分 结构特征 性质 化学式 蒙脱石 含Al3+、Mg2+、OH-、的
硅酸盐中间为铝氧八面体，上下为硅氧四面体的三层片状结构 高离子交换性、强吸附性、吸水膨胀性、多孔结构 (Na，Ca)0.33(Al，Mg)2［Si4O10］(OH)2·nH2O 海泡石 富镁硅酸盐黏 三条条辉石式单链构成的2∶1 结构带和连续的硅氧四面体层 高离子交换性、强吸附性、分散性、多孔结构 (Si12)(Mg8)O30(OH)4(OH2)4·8H2O 沸石 碱金属及碱土金属铝硅酸盐 硅氧四面体、铝氧八面体骨架晶格结构 高离子交换性、表面电负性、催化性、 强吸附性 AmBpO2p·nH2O 高岭土 硅铝酸盐 1∶1型层状硅氧四面体和铝氢氧八面体 吸附性，可塑性，电绝缘性 2SiO2·Al2O3·2H2O 凹凸棒 含有不定量的Na+、Ca2+、Fe3+、Al3+含水富镁铝硅酸盐 具链层状结构
呈毛发状或纤维状的集合体高离子交换性、吸附性、吸水膨胀性、多孔结构 Mg5Si8O20(OH)2(OH2)4·4H2O 
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表 2 处理土壤中重金属的常见纳米材料
Table 2. Common nanomaterials for treating heavy metals in soil
材料名称 重金属 效果 纳米羟基磷灰石羟基磷灰石 Pb、Cu、Cd CaCl2提取态含量降低 生物炭负载纳米羟基磷灰石 Pb 芥兰中Pb含量降低87% 纳米沸石 Cd 比普通沸石吸附量提高12倍 介孔硅纳米材料 Cd Cd有效态最高降低93% 纳米TiO2 Cd、Pb 促进残渣态和可氧化态Cr以及可氧化态和酸可交换态Pb释放 纳米零价铁 As 减少植物对As的吸收
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表 3 不同黏土矿物材料修复效果
Table 3. Repair effect of different clay mineral materials
材料种类 重金属种类 土壤pH值 施加量 修复效果 膨润土 膨润土[38] Cd；Pb 8.2 1%；3%；5% 可交换态Cd、Pb分别降低了11.1%～42.5%；20.3%～49.3% 有机膨润土[39] Cu；Zn - 4% TCLP提取态Cu、Zn降低了77%、99% 铝撑膨润土[40] Cu；Cd；Pb 8.32 2.5% DTPA提取态Cu、Zn降低了28.4%、18.1% 海泡石 海泡石[41] Cd 4.48；6.19；7.76 1%；2%；5% 盆栽试验TCLP-Cd降低0.6%～49.6%，野外实验降低4.0%～32.5% 海泡石-石灰石[42] Cd；Pb 5.39 2、4、6 g/kg 可交换态Cd、Pb降低了99.8%、98.9% 凹凸棒 凹凸棒[43] Cu；Pb；Zn 6.6 - 水提取态Cu、Pb、Zn降低17%、450%、45% 坡缕石[44] Cd；Pb；Cu；Zn 4.63；8.22 2%；5% 降低可交换态Pb>Cd> Cu > Zn 坡缕石-鸟粪石[45] Cd；Pb - 10% 弱酸提取态Cu、Cd降低了47.7%、25.5% 电器石[46] Cd 7.45 1%；2%；5% 显著降低了DTPA提取态Cd 沸石[47] Cd 5.4 15% 吸附Cd从5.2 mg/L下降到0.1mg/L
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