重金属生物有效性在矿山环境评价中应用研究进展

孙晓艳; 罗立强

doi:10.13779/j.cnki.issn1001-0076.2019.01.020

重金属生物有效性在矿山环境评价中应用研究进展

孙晓艳^1,2,,
罗立强^1,2, ,

1.
国家地质实验测试中心，北京 100037

2.
中国地质大学(北京) 地球科学与资源学院，北京 100083

基金项目:
国家重点研发计划项目（2016YFC0600603）；国家高新技术研究发展计划（863）项目（2007AA06Z124）；中国地质调查项目（DD20160340）；国家自然科学基金项目（20775018，41201527）

详细信息

作者简介: 孙晓艳(1981-), 女, 博士研究生, 主要研究方向为生物地球化学和仪器分析, E-mail:sunxiaoyan2020@126.com

通讯作者: 罗立强(1959-), 男, 研究员, 研究方向为生物地球化学, E-mail:luoliqiang@cags.ac.cn

中图分类号: X822.5

收稿日期: 2018-04-25

刊出日期: 2019-02-25

Research Progress on the Application Bioavailability of Heavy Metals to Evaluate Ecological Risk in Mining Area

SUN Xiaoyan^1,2,,
LUO Liqiang^1,2, ,

1.
National Research Center for Geoanalysis, Beijing 100037, China

2.
China University of Geosciences, Beijing 100083, China

More Information

Corresponding author: LUO Liqiang, luoliqiang@cags.ac.cn

Received Date: 25 April 2018

Publish Date: 25 February 2019

摘要

摘要:
重金属的生物有效性是决定重金属生态环境毒性的重要因素。生物有效性可为矿山土壤中重金属风险评价提供可靠的数据，提升评价质量。从厘清生物有效性概念入手，阐述了生物有效性研究方法的特性，评价了生物有效性在矿山环境评价中的应用，以重金属的生物有效性可以更好的评价重金属由土壤迁入植物的生态风险，更科学的确定重金属安全阈值，为矿山环境风险和人体健康风险评价提供新的方法和思路。
- 矿山 /
- 重金属 /
- 生物有效性 /
- 环境污染 /
- 风险评价
Abstract:
While mining activities bring great economic benefits, high heavy metals concentration in soil has negative effects on ecosystems and generate potential health risks to human body. However, the total concentration of heavy metals in soil doesn't represent the fraction available for plants and the toxicty for ecosystems all the time because they accumulate in different geochemical froms. Bioavailability provides accuracy data to mine geological enviroment evaluation and improve the enviroment evaluation quality. Review the application bioavailability of trace metals to evaluation mining area environmental risk, found that bioavailabilty is better predictation of trace metal translocation from soil to crops and derivation of soil criteria of heavy metals, and provides new method for enviroment evaluation.
- mining area /
- heavy metal /
- bioavailability /
- enviroment polltion /
- risk assessment

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表 1 一步提取法的方法特性

Table 1. Examples of extractants for assessing phytoavailable trace element contents of soils

提取剂	目标形态	分析元素	方法特性	文献
NaNO₃	离子交换态	Cr, Ni, Cu, Zn, Cd, Pb	能够反映土壤pH对生物有效性的影响	[22, 23]
CaCl₂	离子交换态	Cr, Ni, Cu, Zn, Cd, Pb	模拟当下进入孔隙水中重金属浓度，Ca²⁺是孔隙水中存在的主要离子，且离子强度与孔隙水中离子强度相近	[23, 26]
NH₄NO₃	离子交换态	Al, Zn, Mo, Ba, Cd, Se, Sr, Cu, Pb, Ni, Hg, Cr, As, Tl, Ca, Mn, Y, La	提取以弱静电引力吸附于土壤组分表面的重金属，分析过程中pH有轻微降低，土壤溶液中离子强度增加。在酸性土壤评估中会出现过度评价，而中性和碱性土壤更为适用，对超富集植物适用性差	[23, 27]
MgCl₂	离子交换态	Cr, Ni, Cu, Zn, Cd, Pb	Mg²⁺的交换容量较强和Cl^-较弱的络合力结合在一起，不分解有机物质、硅酸盐和金属硫化物，有2%~3%的碳酸盐溶解，但是缩短提取时间可以避免，会导致pH降低，引起部分锰氧化物溶解	[21]
NH₄Ac	离子交换态和碳酸盐结合态	Cd, Pb, Cu, Zn, Cr, Ni, As, Cd, Zn, Pb	在非缓冲条件下易发生水解而使pH上升，提取离子交换态，而在pH=4.8的缓冲条件下提取酸溶态效果较好	[28, 29]
HAc	离子交换态和碳酸盐结合态	Ni, Cu, Zn, Cd, Pb	有部分铁氧化物结合态会被释放，造成过度评估	[25]
HCl	离子交换态和酸溶态	Cd, Cu, Cr, Ni, Zn, Pb	随酸浓度增加提取能力增强，0.1 M仅能提取可交换态，但有少量铁锰氧化物结合态被释放。1 M HCl可提取大部分的非残渣态	[26, 30]
HNO₃	酸溶态和部分可还原态	Cd, Cu, Cr, Ni, Zn, Pb	提取能力较强	[25, 26]
LMWOAs	离子交换态	Cr, Cu, Zn, Cd	对酸性、中性和偏碱性新鲜根际土都适用	[31]
EDTA	酸溶态和部分有机结合态	Cr, Ni, Cu, Zn, Cd, Pb	无需严格控制pH	[25, 26]
Mehlich3	酸溶态和部分有机结合态	Co, Ni, Cu, Pb	对酸性和碱性土壤均适用	[28, 32]

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表 2 化学提取法评估重金属迁移到植物的风险

Table 2. Applications of chemical extraction methods for evaluation of the risk of heavy metals in soils migration to plant

元素	土壤和植物	研究方法	研究结果	文献
Cd, Pb, Zn	湖南4个矿区和冶炼厂，大豆	MgCl₂	MgCl₂可提取态Pb和Zn与大豆根茎叶中累积的Pb和Zn存在显著的相关关系(P < 0.01)，Cd与根茎叶种皮和豆子中的Cd均存在显著的相关关系(P < 0.05)	[42]
Pb, Zn	意大利撒丁岛西南矿区和未污染区，3种优势植物	BCR	植物累积的Zn与30~60 cm土壤BCRF1, F2, F3可提取态Zn和Zn总量存在显著的正相关关系，而与表层土壤Zn的各态和Zn总量均不相关，仅一个植物内Pb与30~60 cm土壤BCRF3和残渣态存在相关关系	[4]
As, Cd, Cu, Pb, Zn	广东省南部大宝山矿区，芥菜、水稻、甘蔗	BCR	BCRF1可提取态的Cd、Zn，与水稻谷粒中Cd、Zn的相关系数r²分别为0.78、0.82，与甘蔗茎中相关系数分别为0.35、0.68，与芥菜中相关系数分别为0.69、0.87	[2]
Cd, Cr, Cu, Ni, Pb, Zn	科索沃地区受铅锌矿影响的农田土壤，玉米和西红柿	BCR	BCRF1与玉米中Pb、Ni和Cu的相关系数为0.47、0.75和0.62；与西红柿中Cd相关系数r=0.51。BCRF2与玉米中Cd相关系数r=0.49，与西红柿中的Ni、Cr和Cu的相关系数分别为0.69、0.43和0.46。BCRF3与玉米中的Zn和Cd存在显著相关性，与西红柿中Pb、Ni和Cu存在相关性	[43]
As	石门雄黄矿区，苋菜(盆栽)	Tessier, BCR, Shiowatana	苋菜吸收As的浓度，与对应土壤中As的有效态有显著的相关性，相关系数R²分别为Shiowatana(F_S1+F_S2)：0.93，BCRF1：0.94，Tessier：0.85	[44]
Cd, Cu, Pb, Zn	浙江北部铅锌矿区尾矿污染的水稻田，水稻	Mehlich1, Mehlich3, EDTA, DTPA-TEA, NH₄Ac, CaCl₂	水稻茎叶和水稻谷粒吸收的重金属均存在显著的正相关关系性，其中NH₄Ac(r：0.74~0.96)和CaCl₂(r：0.70~0.89)相关系数最高	[45]
As, Pb	韩国废弃锡、铜和金矿区，印度芥菜(栽培)	CaCl₂, HCl, NH₄H₂PO₄, 王水	CaCl₂, HCl, NH₄H₂PO₄提取的有效态和王水提取的总量与印度芥菜中As的相关系数r²分别为0.71, 0.67, 0.24和0.23；与Pb的相关系数r²分别为0.56, 0.60, 0.20和0.18	[40]
Al, Mn, Pb, Zn	葡萄牙废弃铅矿，8种植物	H₂O, CaCl₂, Ca(NO₃)₂, NH₄Ac, DTPA	多种元素生物有效性研究结果表明CaCl₂可提取态反映了更多的植物种类和元素种类的植物有效性	[46]
Co, Cr, K, Mn, Na, Ni, Pb, Zn	锡矿，印度芥菜	DTPA, EDTA, NH₄NO₃, CaCl₂, NaNO₃	印度芥菜中Pb、Cr与各个提取法提取的土壤中Pb和Cr之间存在显著的相关关系	[47]
As, Cd, Pb, Zn, Sb	冶炼厂和矿山，菜豆苗(栽培)	EDTA, DTPA, NH₄NO₃, CaCl₂, NaNO₃	菜豆苗中累积重金属与CaCl₂, NH₄NO₃和Ca(NO₃)₂存在显著正相关关系，Pb与提取能力更强的EDTA、DTPA和HAc等提取剂的可提取态存在显著的相关性	[41]
As, Sb	澳大利亚尤郎佳废弃Sb冶炼厂，萝卜	DGT, Wenzel, H₂O	萝卜根和茎叶中累积的As和Sb与3种提取法可提取态As和Sb的量存在极显著的相关关系，线性回归方程r²=0.96~0.99	[48]

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