Simultaneous Determination of Silver, Boron and Tin in Carbonate Minerals by Alternating Current-Arc Optoelectronic Direct Reading-Emission Spectrometry
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摘要: 银硼锡元素的丰度和变化特征可以反映区域成矿条件，指示矿床或矿化存在。碳酸盐矿物中的银硼锡是勘查地球化学及多目标地球化学中的必测元素，其测定方法是地球化学元素配套分析方案中必不可少的方法之一。由于碳酸盐矿物与普通的岩石、土壤和水系沉积物不同，该类矿物主要是灰岩、白云岩等含钙和镁元素比较高的岩石类样品，同时测定样品中银硼锡的技术难点在于高含量钙镁基体会严重干扰低含量待测元素，且摄谱过程中由于易产生二氧化碳造成样品飞溅。针对碳酸盐矿物的特殊性，本文建立了交流电弧-光电直读发射光谱同时测定碳酸盐矿物中银硼锡的分析方法。通过优化样品前处理及实验条件，用10%的盐酸处理样品，消除了基体元素钙和镁的干扰；以锗（Ge）作为内标元素进行定量，可以消除因电弧激发条件变化以及试样基体组分等外部因素造成干扰的影响；采用银与长波锗元素组成分析线对，硼和锡与短波锗元素组成分析线对，灵敏度较好；选择天然碳酸盐岩石与人工合成灰岩等12种国家一级地球化学标准物质作为标准系列，使基体组分与样品相类似；采用分析线和内标线同时扣背景的离线差减法进行背景校正。结果表明：该方法对银硼锡的检出限分别为0.008、0.49、0.18μg/g；方法精密度（RSD）对银大于10%，其余均优于10%；经国家一级地球化学标准物质验证，银硼锡测定平均值与认定值的对数差值（△lgC）均小于或等于±0.05，满足多目标区域地球化学调查规范的要求。Abstract:
BACKGROUND The abundances and variation characteristics of silver, boron and tin reflect the regional metallogenic conditions and indicate the existence of deposits or mineralization. Silver, boron and tin in carbonate minerals are elements that must be determined in exploration geochemistry and multi-objective geochemistry. The analytical method was one of the essential methods in the matching analysis scheme of geochemical elements. Because carbonate minerals are different from common rocks, soils and water-based sediments, these minerals are mainly limestone, dolomite and other rock samples with relatively high calcium and magnesium elements, and the technical difficulty in determining silver, boron and tin in these samples is that the high content of calcium and magnesium matrix will seriously disturb the elements with low contents to be measured, and the sample is easily contaminated due to carbon dioxide during the spectrum recording process. OBJECTIVES To solve the problems of rapid and accurate determination of silver, boron and tin in carbonate minerals. METHODS In view of the particularity of carbonate minerals, an analytical method for the simultaneous determination of silver, boron and tin in carbonate minerals by alternating current-arc optoelectronic direct reading-optical spectrometry (AC-Arc-OES) was established. RESULTS By using 10% hydrochloric acid to digest the sample, the interference of matrix elements, calcium and magnesium, was eliminated. Germanium was used as the internal standard element for quantitative analysis, which eliminated the influence of external factors, such as the change of arc excitation conditions and matrix composition of the sample. The silver element and the long wave germanium element were used to form the analysis line pair, and the boron and tin element and the short wave germanium element were used to form the analysis line pair with good sensitivity. Twelve national geochemical reference materials, such as natural carbonate rock and synthetic limestone, were selected as the standard series. The matrix components were similar to those of the samples. The method of off-line subtraction was used to correct the background. The detection limits of the method for silver, boron and tin were 0.008μg/g, 0.49μg/g and 0.18μg/g, respectively. The precision of the method was larger than 10% for silver, and that of other elements was better than 10%. The accuracy of the method was verified by the national level geochemical reference materials, and the logarithm difference between the average value and the certified value of the reference materials was less than or equal to ±0.05. CONCLUSIONS This method was used to solve the problem of rapid determination of silver, boron and tin in carbonate minerals. It is simple and fast, and suitable for the determination of a large numbers of samples. All of the technical indices of the method meet the requirements of multi-objective regional geochemical survey specifications. -
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表 1 地球化学标准物质及银硼锡含量
Table 1. Geochemical standard substances and content of Ag, B and Sn
标准物质编号 标准物质类型 待测元素含量(μg/g) Ag B Sn GBW07129 碳酸盐岩石 0.016 1.3 0.7 GBW07128 碳酸盐岩石 0.021 2.2 0.6 GBW07131 碳酸盐岩石 0.016 6.4 0.7 GBW07136 碳酸盐岩石 0.022 47.7 0.6 GBW07712 合成灰岩 0.030 2.2 0.28 GBW07713 合成灰岩 0.060 5.2 0.58 GBW07714 合成灰岩 0.11 10 1.1 GBW07715 合成灰岩 0.21 20 2.1 GBW07716 合成灰岩 0.51 50 5.1 GBW07717 合成灰岩 1.0 100 10 GBW07718 合成灰岩 2.0 200 20 GBW07719 合成灰岩 5.0 500 50 
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表 2 方法的分析线对
Table 2. Analytical line pairs of the method
待测元素 分析线波长
(nm)内标线波长
(nm)Ag Ag 328.0683 Ge 326.9494 B B 249.7733 Ge 270.9626 Sn Sn 283.9649 Ge 270.9626
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表 3 方法精密度
Table 3. Precision tests of the method
标准物质
编号Ag B Sn 测定值
(μg/g)RSD
(%)测定值
(μg/g)RSD
(%)测定值
(μg/g)RSD
(%)GBW07127 0.021 10.52 1.87 3.53 0.69 5.89 GBW07131 0.018 11.31 6.36 2.23 0.71 5.42 GBW07135 0.044 8.20 14.77 1.85 1.11 5.12
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表 4 方法准确度
Table 4. Accuracy tests of the method
待测元素 项目 GBW07127 GBW07130 GBW07131 GBW07132 GBW07133 GBW07134 GBW07135 GBW07136 认定值(μg/g) 0.02 0.013 0.016 0.019 0.029 0.035 0.045 0.022 Ag 平均值(μg/g) 0.021 0.014 0.018 0.022 0.032 0.034 0.044 0.024 ΔlgC 0.02 0.04 0.04 0.05 0.04 -0.01 -0.01 0.03 认定值(μg/g) 1.9 1.47 6.4 3.7 3.1 2.3 14.8 47.7 B 平均值(μg/g) 1.87 1.45 6.36 3.68 3.19 2.29 14.77 48.10 ΔlgC -0.01 -0.01 0.00 0.00 0.01 0.00 0.00 0.00 认定值(μg/g) 0.7 0.5 0.7 0.6 0.5 0.9 1.1 0.6 Sn 平均值(μg/g) 0.69 0.53 0.71 0.57 0.46 0.94 1.11 0.56 ΔlgC 0.00 0.03 0.00 -0.03 -0.04 0.02 0.00 -0.03
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