污染土壤中重金属形态分析及相关模型

刘泽浩; 贾春云; 范凤翠; 代淑娟; 李晓军

doi:10.12476/kczhly.202412260677

污染土壤中重金属形态分析及相关模型

1.
中国科学院沈阳应用生态研究所，辽宁　沈阳　110016

2.
河北省农林科学院农业信息与经济研究所精准农业研究室，河北　石家庄　050050

3.
辽宁科技大学矿业工程学院，辽宁　鞍山　114051

基金项目: 国家重点研发计划课题（2024YFC3712603）；中国科学院战略性先导科技专项（XDA28060302）；辽宁省科技计划联合计划（应用基础研究）项目（2023021253-JH2/1017）；沈阳市社会治理科技专项（24-213-3-10）

详细信息

作者简介: 刘泽浩（1995-），男，硕士研究生，主要从事污染土壤修复

通讯作者: 贾春云（1981-），女，博士，副研究员，研究方向为污染土壤修复。

中图分类号: TD989

收稿日期: 2024-12-26

刊出日期: 2025-06-25

Speciation Analysis and Related Models of Heavy Metals in Contaminated Soil

1.
Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, Liaoning 110016, China

2.
Hebei Academy of Agriculture and Forestry Sciences, Precision Agriculture Research Office of Agricultural Information and Economics Research Institute, Shijiazhuang, Hebei 050050, China

3.
School of Mining Engineering, Liaoning University of Science and Technology, Anshan, Liaoning 114051, China

More Information

Corresponding author: JIA Chunyun, jiachunyun@iae.ac.cn

Received Date: 26 December 2024

Publish Date: 25 June 2025

摘要

摘要:
土壤重金属污染问题越来越突出，长期累积改变土壤生态环境质量，影响作物生长并威胁人类健康，因此亟须修复。污染土壤修复前，首先要了解重金属的来源与分布特点，尤其是赋存形态。重金属具有不同形态，每种形态对应相应的提取步骤。五步提取法、BCR等都是常见的重金属提取方法。土壤重金属测定方法包括原子荧光光谱法、原子吸收光谱法、电感耦合等离子体发射光谱法等。为了更好地了解和预测土壤中重金属的形态分布特征，需要合理应用土壤重金属的化学形态分析模型，包括经验模型、机理模型和多表面形态模型，这些模型分析可以更有效地模拟土壤中的重金属形态分布及变化趋势，为重金属污染土壤修复提供重要依据。
- 污染土壤 /
- 重金属提取 /
- 形态分析 /
- 模型预测
Abstract:
The problem of heavy metals contaminated soil is becoming more and more prominent. Long-term accumulation of heavy metals changed the quality of soil ecological environment, and then influenced crop growth and human health. Therefore, it is urgently necessary to restore heavy metal polluted soil. Before remediating of contaminated soil, we must understand clearlythe source and distribution of heavy metals, especially the heavy metal speciation. Heavy metals in soil have different forms, and each form has a corresponding extraction procedure. Five-step extraction method, BCR, etc. are common heavy metal extraction methods. Conventional methods for the determination of heavy metal ions in soil generally include atomic fluorescence spectrometry, atomic absorption spectrometry, inductively coupled plasma emission spectrometry, etc.. In order to better understand and predict the morphological distribution characteristics of heavy metals in soil, it is rationally necessary to use chemical speciation analysis models of heavy metals in soil, including empirical models, mechanism models and multi-surface morphological models, which can efficiently simulate the morphological distribution and changing trend of heavy metals in soil. It provides an important basis for the remediation of heavy metal-contaminated soils.
- polluted soil /
- heavy metal extraction /
- morphological analysis /
- model prediction

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图 1 重金属的超标比例

Figure 1.

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图 2 其他学者提出的重金属形态分类

Figure 2.

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表 1 五步连续提取法

Table 1. Five-step continuous extraction method

形态	步骤
可置换态	① 取1.00 g样品置于8 mL MgCl₂溶液中（1 mol/L，pH=7），18 ℃环境下振荡1 h（200 r/min），然后离心 30 min（4 000 r/min），倒出上清液，备用测样，保留沉淀。
碳酸盐结合态	② 取①中的沉淀置于8 mL NaAc溶液中（1.0 mol/L，pH=5），20 ℃环境下振荡1.5 h（200 r/min），然后以 100 r/min速度振荡16 h，离心0.5 h（4 000 r/min），倒出上清液，备用测样，保留沉淀。
铁-锰氧化物结合态	③ 取②中的沉淀置于20 mL NH₂·HAc溶液中，96 ℃环境下保持3 h（每10 min搅拌），离心0.5 h （4 000 r/min），倒出上清液，备用测样，保留沉淀。
有机物结合态	④ 取③中的沉淀置于3 mL HNO₃溶液中（0.02 mol/L），然后加5 mL H₂O₂（30%），83 ℃环境下保持 1.5 h（每10 min搅拌），之后追加3 mL H₂O₂（30%），继续83 ℃环境下保持1.1 h（每10 min搅拌）；然后冷却，加5 mL NH₄Ac溶液，20 ℃环境下静置10 h，倒出上清液，备用测样，保留沉淀。
残渣态	⑤ 将④沉淀置于聚乙烯坩埚中，混酸消解。

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表 2 BCR三步连续提取法

Table 2. BCR three-step continuous extraction method

形态	步骤
水溶态	① 取1.00 g样品置于25 mL 蒸馏水中，22 ℃环境下振荡2 h，然后离心20 min（3 000 r/min），倒出上清液，备用测样，保留沉淀。
弱酸提取态	② 取1.00 g样品置于40 mL MHOAc溶液中，22 ℃环境下振荡16 h，然后离心20 min（3 000 r/min），倒出上清液，备用测样，保留沉淀。
可还原态	③ 取②中的沉淀置于 40 mL HOAc·HCl溶液中（0.5 mol/L，pH=2），22 ℃环境下振荡16 h，然后离心20 min （3 000 r/min），倒出上清液，备用测样，保留沉淀。
可氧化态	④ 取③中的沉淀置于10 mL H₂O₂（30%）中，常温下静置1 h后，放入水浴锅加热至85 ℃，水浴1 h后，加 50 mLNH₄Ac溶液，22 ℃环境下振荡16 h，离心20 min（3 000 r/min），倒出上清液，备用测样，保留沉淀。
残渣态	⑤ 将④沉淀置于聚乙烯坩埚中，混酸消解。

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表 3 重金属砷（As）的提取方法步骤

Table 3. Extraction method steps of heavy metal arsenic (As)

形态	步骤
交换态砷	①取1.00 g样品置于25 mL NH₄Cl溶液（1 mol/L）中，2 ℃环境下振荡0.h（150 r/min）后，离心3 min （4 000 r/min），取上清液过滤，上机测样，沉淀置于25 mL NaCl溶液中，常温振荡20 min，离心，倒出上清液，保留沉淀。
铝型砷(Al-As)	②取①中处理后的沉淀置于25 mL NH溶液(0.5 mol/L)中，25 ℃环境下振荡1 h（150 r/min）后，离心3 min （4 000 r/min），取上清液过滤，上机测样，沉淀置于25 mL NaCl溶液中，常温振荡20 min，离心，倒出上清液，保留沉淀。
铁型砷(Fe-As)	③ 取②中处理后的沉淀置于25 mL NaOH溶液(0.1 mol/L)中，常温振荡2 h（150 r/min）后，静置16 h，然后继续常温振荡2 h（150 r/min）然后以硝酸调节至中性，离心10 min后（4 000 r/min），取上清液过滤，上机测样，沉淀置于25 mL NaCl溶液中，常温振荡20 min，离心，倒出上清液，保留沉淀。
钙型砷(Ca-As)	④ 取③中处理后的沉淀置于25 mL H₂SO₄溶液（0.25 mol/L）中, 25 ℃环境下振荡1 h（150 r/min）后，离心5 min （4 000 r/min），取上清液过滤，上机测样，沉淀置于25 mL NaCl溶液中，常温振荡20 min，离心，倒出上清液，保留沉淀。
残渣态砷(Res-As)	⑤ 取④中处理后的沉淀置于8 mL现配王水中（25 mL比色管），然后水浴消解2 h（95 ℃），冷却至室温后，定容至25 mL，摇匀；然后取其8 mL，加2 mL VC-硫脲溶液摇匀，静置15 min。

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表 4 重金属常用的测定方法原理及优缺点

Table 4. Principles and advantages and disadvantages of commonly used determination methods for heavy metals

方法	仪器	原理	优缺点
原子荧光法	原子荧光光谱仪 (AFS)	利用原子在辐射能的作用下，从而放射出的荧光，根据其强度来对土壤中重金属作定量分析	可以设计多通道结构，从而实现同时测定多个元素。
原子吸收法	原子吸收光谱仪 (AAS)	利用特殊的光源发出具有原子可吸收的特征谱线的光，根据光的衰减程度对检测到的重金属进行定量分析	1、精确度高。高浓度元素检测中使用火焰法的标准偏差系数＜1%。采用石墨炉法精确度一般可达95%～97%。 2、可以测定非金属元素和有机质。
电感耦合等离子体发射法	发射光谱仪 (ICP)	使用电感耦合等离子体炬作为光源，根据激发态原子回到基态时所发射出的特征光谱来定量分析重金属元素	1、简单高效，测定的元素较广。 2、精度高，检出限低， 3、可智能调整空气流速，减少积碳危害。
激光诱导击穿法	激光诱导击穿光谱仪 (LIBS)	利用激光，在样品表面形成激光等离子体，从而样品发光，根据其光谱进行定量分析	1、能分析多种元素基本形态多样性。 2、简化了样品制备过程，能够直接迅速对样品分析，并且可测定的元素多。
X射线荧光法	X射线荧光摄谱仪 (XRF)	根据辐射所能激发的基态分子所发出的荧光强度变化的来进行定量分析	分辨率高，适应性广。

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