手持式XRF在土壤调查修复项目中应用的可靠性分析

孙中瑾; 张莹莹; 叶小瑭; 李新元; 满伟慧; 刘超; 史瑞; 刘敬兵; 王子鸣

doi:10.12153/j.issn.1674-991X.20230715

手持式XRF在土壤调查修复项目中应用的可靠性分析

doi: 10.12153/j.issn.1674-991X.20230715

孙中瑾^{1, 2, 3,},
张莹莹^{1, 2},
叶小瑭¹,
李新元¹,
满伟慧^{1, 2},
刘超^{1, 2},
史瑞^{1, 2, ,},
刘敬兵⁴,
王子鸣³

1.
山东省鲁南地质工程勘察院(山东省地质矿产勘查开发局第二地质大队)
2.
自然资源部采煤沉陷区综合治理工程技术创新中心
3.
山东省地矿建设有限公司
4.
山东省物化探勘查院

详细信息

作者简介:
孙中瑾（1990—），男，注册土木工程师（岩土），硕士，主要从事水文地质、工程地质和环境地质研究，1140860142@qq.com

通讯作者:
史瑞（1986—），女，高级工程师，硕士，主要从事土壤污染调查与修复研究，shirui1986@whu.edu.cn

中图分类号: X833
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出版历程
- 收稿日期: 2023-10-08
- 录用日期: 2024-01-31
- 修回日期: 2023-12-05
- 网络出版日期: 2024-03-08

Reliability analysis of handheld XRF application in soil investigation and remediation projects

SUN Zhongjin^{1, 2, 3
,},
ZHANG Yingying^{1, 2},
YE Xiaotang¹,
LI Xinyuan¹,
MAN Weihui^{1, 2},
LIU Chao^{1, 2},
SHI Rui^{1, 2
, ,},
LIU Jingbing⁴,
WANG Ziming³

1.
Shandong Provincial Lunan Geology and Exploration Institute (Shandong Provincial Bureau of Geology and Mineral Resources No.2 Geological Brigade)
2.
Technology Innovation Center of Restoration and Reclamation in Mining Induced Subsidence Land, Ministry of Natural Resources
3.
Shandong Provincial Geology Construction Co., Ltd.
4.
Shandong Institute of Geophysical & Geochemical Exploration

摘要

摘要:
为确定手持式X射线荧光光谱仪（XRF）测量精度和准确度是否能够满足土壤环境快速检测要求，以山东省济宁市某地块土壤污染状况调查项目为背景，分别采用XRF快速检测仪检测和实验室检测方法对浅层土层（0.2~0.5 m）和深层土层（1.5~2.0 m）样品中砷（As）、铜（Cu）、铅（Pb）、锌（Zn）和镍（Ni）5种元素浓度进行检测。结果表明：浅层土层重金属As的XRF检测值普遍高于实验室检测值，Cu、Pb、Zn、Ni的XRF检测值普遍低于实验室检测值，误差普遍在±30%以内；浅层土层的重金属元素XRF检测值与实验室检测值普遍相对偏差（RD为−33.82%~23.53%）及总体相对偏差标准差（6.79~19.52）小于深层土层（分别为−30.26%~98.36%、9.53~49.77），相对偏差的离散程度小于深层土层；浅层土层的重金属的决定系数（R²为0.776 2~0.954 9）普遍高于深层土层（R²为0.776 2~0.954 9），相关性高于深层土层。野外使用XRF对土壤样品中重金属进行检测时，所取的土壤样品尽量避免大颗粒，对样品待测面进行压实、压平处理，对于含水率高的样品应适当进行干燥处理，以降低检测误差。虽然手持式XRF检测存在一定误差，但在土壤污染状况调查项目中可以较好地反映土壤元素浓度范围，具有较高的可靠性，可以满足项目土壤快速检测需求。
- X射线荧光光谱仪（XRF） /
- 重金属 /
- 土壤污染状况 /
- 快速检测 /
- 可靠性
Abstract:
In order to determine whether the measurement precision and accuracy of the handheld X-ray fluorescence spectrometer (XRF) can meet the requirements of rapid detection of soil environment, in the context of one soil pollution survey project in a certain plot of Jining City, Shandong Province, the concentrations of arsenic (As), copper (Cu), lead (Pb), zinc (Zn), and nickel (Ni) were detected by XRF rapid detection and laboratory methods. The samples were collected from shallow soil layers (0.2-0.5 m) and deep soil layers (1.5-2.0 m). The results indicated that for shallow soil layers, XRF measurements of heavy metal As consistently exceeded laboratory data, while XRF measurements of heavy metals Cu, Pb, Zn, and Ni were lower within an error of ±30% compared to laboratory measurements. The relative deviations (RD) and overall relative deviation standard deviations of heavy metal elements in shallow soil layers (RD: −33.82%-23.53%, standard deviation: 6.79-19.52) were generally smaller than those in deep soil layers (RD: −30.26%-98.36%, standard deviation: 9.53-49.77), and the dispersion degree of relative deviation in shallow soil layers was smaller than that of deep soil layers. Moreover, the determination coefficients (R²) for heavy metals in shallow soil layers (R²: 0.7762-0.9549) were consistently higher than those in deep soil layers (R²: 0.7762-0.9549), indicating a stronger correlation. When XRF was employed for in-field detection of heavy metals in soil samples, it was recommended to avoid large particles in the samples, compact and flatten the testing surface and, for samples with high moisture content, carry out appropriate drying to minimize detection errors. Despite the inherent limitations of handheld XRF detection, the method demonstrates acceptable accuracy and reliability in reflecting the concentration range of soil elements in soil pollution survey projects, meeting the rapid detection requirements of such projects.
- X-ray fluorescence spectrometer (XRF) /
- heavy metals /
- soil pollution status /
- quick detection /
- reliability

HTML全文

图 1 XRF的2种基本类型

Figure 1. Two basic types of X-ray fluorescence spectrometer

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图 2 浅层土壤XRF与实验室检测重金属浓度对比

Figure 2. Comparison of XRF and laboratory detection of heavy metal concentrations in shallow soil

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图 3 深层土壤XRF与实验室检测重金属浓度对比

Figure 3. Comparison of XRF and laboratory detection of heavy metal concentrations in deep soil

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图 4 XRF法与实验室检测土壤重金属浓度相对偏差标准差

Figure 4. Standard deviation of relative deviation between XRF and laboratory detection of soil heavy metal concentrations

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图 5 实验室与XRF法测定浅层土壤重金属的相关性

Figure 5. Correlation between laboratory and XRF methods for determining heavy metals in shallow soil

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图 6 实验室与XRF法测定深层土壤重金属的相关性

Figure 6. Correlation between Laboratory and XRF methods for determining heavy metals in deep soil

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表 1 XRF检测值与实验室检测值相对偏差标准差

Table 1. Standard deviation of relative deviation between XRF detection values and laboratory detection values

重金属	浅层土层		深层土层
重金属	RD/%	相对偏差标准差	RD/%	相对偏差标准差
As	−33.82~31.17	19.52	−30.26~98.36	49.77
Cu	−29.63~0.00	9.93	−25.81~5.56	9.53
Pb	−23.08~23.53	16.19	−27.59~25.00	19.69
Zn	−22.22~0.00	6.79	−20.97~16.36	9.95
Ni¹⁾	−38.27~−10.53	11.13	−38.78~12.50	15.10
1) Ni在浅层土层仅3#、10#和11#样本及深层土层16#、21#和23#样本相对偏差下限低于−30%。

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表 2 重金属元素的XRF检测值与实验室检测值拟合结果

Table 2. Fitting results of XRF detection values and laboratory detection values of heavy metal elements

重金属	浅层土层				深层土层
重金属	线性方程	R²	相关性	准确度	线性方程	R²	相关性	准确度
As	y=1.051 6x	0.7762	强	筛选性	y=1.101 7x	0.542 9	中等	定性筛选性
Cu	y=0.747 2x	0.926 2	极强	确定性	y=0.794 6x	0.955 3	极强	确定性
Pb	y=0.898 2x	0.863 6	极强	确定性	y=0.908 5x	0.670 4	强	定性筛选性
Zn	y=0.877 6x	0.954 9	极强	确定性	y=0.944 8x	0.929 7	极强	确定性
Ni	y=0.673 1x	0.916 9	极强	确定性	y=0.760 7x	0.695 5	强	定性筛选性
注：x为实验室检测值、y为XRF检测值；浅层土层样本数为11，深层土层样本数为12。

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表 3 实验室检测值与XRF检测值数据偏差统计

Table 3. Statistical table for deviation between laboratory test values and XRF data

重金属	浅层土层		深层土层
重金属	偏差绝对值最大值	均方根误差	偏差绝对值最大值	均方根误差
As	2.4	1.44	6.3	3.33
Cu	13.0	2.19	11.0	1.89
Pb	6.0	3.41	9.0	4.07
Zn	18.0	7.73	13	6.01
Ni	31.0	10.24	19.0	4.76

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