X射线荧光光谱法分析地质样品的应用技巧

陈静; 高志军; 陈冲科; 刘延霞; 张明炜

doi:10.15898/j.cnki.11-2131/td.2015.01.012

X射线荧光光谱法分析地质样品的应用技巧

1.
河南省岩石矿物测试中心, 河南郑州 450012

2.
国土资源部贵金属分析与勘察技术重点实验室, 河南郑州 450012

详细信息

作者简介: 陈静, 工程师, 从事X射线荧光光谱分析及化学分析测试.E-mail:liminggui@126.com

中图分类号: O657.31

收稿日期: 2014-06-04

修回日期: 2014-12-16

录用日期: 2015-01-12

刊出日期: 2015-01-25

Application Skills on Determination of Geological Sample by X-ray Fluorescence Spectrometry

1.
Henan Province Rock and Mineral Testing Center, Zhengzhou 450012, China

2.
Key Laboratory of Ministry and Resources Analysis and Exploration of Precious Metals, Zhengzhou 450012, China

Received Date: 04 June 2014

Revised Date: 16 December 2014

Accepted Date: 12 January 2015

Publish Date: 25 January 2015

摘要

摘要:
X射线荧光光谱法(XRF)具有制样简单、绿色环保、可同时测定多个元素等特点, 被广泛应用于勘查地球化学分析领域中, 其中粉末压片XRF是快速经济的主导方法.然而在大批量实际样品测试中, 如果分析者选择测量条件不当或者校正标准曲线不合理, 就会导致测量结果的粗大误差甚至测出不合逻辑的数据.本文对地质样品中的主要元素在测试中容易出现的技术问题作一具体分析:以钒元素为例, 用实验说明探测器的选择对于测量结果的重要性, 采用SC探测器可将V Kα线与Ti Kβ线分开, 而采用SC+PC探测器两元素的谱线发生重叠; 以硅酸盐中铁元素为例, 描述了不同的回归标准曲线对测量结果的影响; 对地质样品中低含量铌、钽的测定, 标准曲线要根据实际情况合理回归, 并将测试后的样品与化学方法对照, 结果相符.同时提出了硅酸盐、碳酸盐等地质样品的测量问题.对于土壤、水系沉积物、岩石地质样品, 一些元素之间会产生相互干扰, 以常见的造岩元素钛为例, 用实验证明铝和铁对钛的谱线确实有增强和吸收效应; 对于常见的碳酸盐类样品, 氯和铬的测量要考虑氧化钙的吸收增强效应, 必须添加氧化钙作为其吸收增强校正项, 才能保证测量结果可靠.针对硫元素的测定, 除了受到硫赋存状态的影响, 样品污染问题也是影响因素之一, 需要避免空气、实验室环境以及分析过程中对样品的污染.本文针对一些典型元素XRF分析提出的具体测量方案, 应用于实际地质样品测试可以获得满意的效果.
- 地质样品 /
- X射线荧光光谱法 /
- 测量条件 /
- 标准曲线 /
- 校正项
Abstract:
X-ray Fluorescence Spectrometry (XRF) has such advantages as simple sample preparation, green environmental protection and the simultaneous determination of multiple elements and is widely used in the exploration geochemistry analysis field. Pressed Powder X-ray Fluorescence is the dominant method for its rapid and economic application. However, when large quantities of samples are being tested, if the analysts' measurements conditions are improperly selected or the working curve correction is unreasonable, gross error will be caused in the measurement result. The technology problems encountered in the test of a certain element in geological samples is given a detailed analysis and discussed in this paper. Vanadium is chosen as an example, indicating that the choice of SC detector expounds the importance of correct selection of measurement conditions. For example, the detection of iron in silicate describes the effect of regression curves which work differently on the measurement results. For the determination of low content of niobium and tantalum in geological samples, work curves should be reasonably returned according to the practical situation, and the samples after testing should be compared with chemical methods, then the result can be considered as consistent. In soil, stream sediment, rocks and other geological samples, mutual interference between elements exists. The common rock forming element titanium was used as an example to prove that aluminum and iron in samples does have the absorption and enhancement effect on the spectral lines of titanium. For common carbonate samples, in the measuring of chloride and chromium the enhanced absorption effect of calcium oxide must be considered, and calcium oxide must be added as its enhanced absorption correction term, in order to ensure reliable measurement results. Finally, the problem of pollution of sulfur and the preventive measures were also analyzed. Some common measurement problem of silicate, carbonate in geological samples is presented, and the solution to the actual production is discussed.
- geological sample /
- X-ray Fluorescence Spectrometry /
- measurement conditions /
- standard curve /
- correction term

HTML全文

图 1 用SC探测器和SC+PC探测器测量钒的2θ角扫描谱图

Figure 1.

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图 2 修正前后元素铁的标准曲线

Figure 2.

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图 3 低含量铌和钽的标准曲线

Figure 3.

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图 4 钛的标准曲线

Figure 4.

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图 5 氯和铬的标准曲线

Figure 5.

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表 1 分成三段的铁的回归方程和计算范围

Table 1. The regression equation divided into three sections and the calculated range of Fe

计算方程式	含量范围(%)
w(Fe)=-3.988I²(Fe)+12.221I(Fe)+0.0585	低含量段0~5
w(Fe)=-0.382I²(Fe)+7.798I(Fe)+1.289	中含量段5~22.5
w(Fe)=-0.068I²(Fe)+4.176I(Fe)+9.186	高含量段22.5~80

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表 2 经修正的铁的回归方程和计算范围

Table 2. The modified regression equation and the calculated range of Fe

计算方程式	含量范围(%)
w(Fe)=9.09I(Fe)+0.53	低含量段0~5
w(Fe)=6.616I(Fe)+1.82	中含量段5~22.5
w(Fe)=-0.068I²(Fe)+4.176I(Fe)+9.186	高含量段22.5~80

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表 3 实际样品分析结果比对

Table 3. Comparison of analytical results of actual samples

样品编号	Ta含量(μg/g)		样品编号	Ta含量(μg/g)
样品编号	本方法	ICP-MS法	样品编号	本方法	ICP-MS法
1	30.4	30.6	6	31.05	31.15
2	31.02	31.33	7	29.65	29.88
3	36.35	36.42	8	31.55	31.64
4	38.55	38.7	9	32.45	32.37
5	31.2	31.15	10	29.75	29.88

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表 4 方法精密度

Table 4. Precision tests of the method

标准物质编号	Th含量(μg/g)		RSD (%)	测定次数
标准物质编号	平均含量	标准偏差	RSD (%)	测定次数
GBW 07408	11.9	0.63	5.31	10
GBW 07424	11.63	0.47	4.04	10
GBW 07427	11.31	0.84	7.42	10

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X射线荧光光谱法分析地质样品的应用技巧

1. 河南省岩石矿物测试中心, 河南 郑州 450012 2. 国土资源部贵金属分析与勘察技术重点实验室, 河南 郑州 450012

作者简介: 陈静, 工程师, 从事X射线荧光光谱分析及化学分析测试.E-mail:liminggui@126.com

Application Skills on Determination of Geological Sample by X-ray Fluorescence Spectrometry

1. Henan Province Rock and Mineral Testing Center, Zhengzhou 450012, China 2. Key Laboratory of Ministry and Resources Analysis and Exploration of Precious Metals, Zhengzhou 450012, China

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目录

1.
河南省岩石矿物测试中心, 河南郑州 450012

2.
国土资源部贵金属分析与勘察技术重点实验室, 河南郑州 450012

1.
Henan Province Rock and Mineral Testing Center, Zhengzhou 450012, China

2.
Key Laboratory of Ministry and Resources Analysis and Exploration of Precious Metals, Zhengzhou 450012, China