Determination of Beryllium and Major Elements in Beryllium Ores by Inductively Coupled Plasma-Optical Emission Spectrometry with Lithium Metaborate Fusion
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摘要:
广泛赋存在花岗伟晶岩和热液石英脉中的铍矿石是铍最重要的矿物载体，目前铍矿石系统分析仍以传统化学法为主，影响分析效率，亟待开发一种简单高效的铍矿石中多元素分析方法。本文建立了一种基于偏硼酸锂熔融-电感耦合等离子体发射光谱(ICP-OES)测定铍矿石中铍及主量元素的定量分析方法，使用4∶1熔剂-样品比，950℃下熔融15min后，通过超声提取制备溶液。偏硼酸锂熔融法能有效地分解铍矿石中的氧化物，克服了传统酸溶或碱熔无法检测硅、钠、钾等元素的局限。本方法通过校准曲线与样品基体匹配，加入铕作内标等措施消除基体效应，实现了各元素(以氧化物计)低至0.003%～0.2%的检出限，满足铍精矿质量检测需求。对绿柱石、香花石、日光榴石样品(BeO含量范围为0.14%～13.33%)测定的相对标准偏差(RSD)小于6.83%，与混合酸酸溶分析方法的测定值相对偏差为0.06%～21.28%。通过标准物质GBW07150、GBW07151和GBW07183验证，本方法精密度和准确度均符合地质矿产实验室测试质量管理规范，适用于多种类型铍矿石样品中铍及主量元素的快速连续分析。
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关键词:
- 铍矿石 /
- 铍 /
- 主量元素 /
- 偏硼酸锂 /
- 电感耦合等离子体发射光谱法
Abstract:At present, the systematic analysis method of beryllium ores is still dominated by the traditional chemical method, which seriously affects the analytical efficiency. It is necessary to develop a simple and efficient multi-element analysis method in beryllium ores. We establish a quantitative analysis method for beryllium and principal elements in beryllium ores based on lithium metaborate fusion-inductively coupled plasma-optical emission spectrometry (ICP-OES) to overcome the limitations of the traditional acid solubilization or alkaline fusion that cannot detect elements such as silicon, sodium and potassium. The method involves mixing the flux and the sample in a 4∶1 ratio, melting at 950℃ for 15min, and preparing solutions through ultrasonic extraction. The matrix effect is eliminated by matrix matching and adding europium (Eu) as the internal standard. The content of beryllium oxide in the experimental sample is between 0.14% and 13.33%. The experimental results show that the precision and accuracy of this method meet the quality control requirements in the quality management specification of the geological and mineral laboratory. It is suitable for the continuous and rapid determination of beryllium and major elements in many types of beryllium ore samples such as beryl, hsianghualite and helvine.
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表 1 分析元素、内标元素谱线及观测方式
Table 1. Characteristic wavelengths of analytical elements, internal standard elements and observation mode
元素 谱线(nm) 观测方式 元素 谱线(nm) 观测方式 Al 308.215 径向 Mn 257.610 轴向 Be 313.107 径向 Na 589.592 径向 Ca 317.933 径向 P 213.617 轴向 Fe 259.939 径向 Si 251.611 径向 K 776.490 径向 Ti 334.940 轴向 Mg 279.553 径向 Eu 412.970 径向 
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表 2 方法检出限和测定下限
Table 2. Detection limit and determination limit of the method
成分 检出限
(%)测定下限
(%)成分 检出限
(%)测定下限
(%)Al2O3 0.06 0.20 MnO 0.005 0.02 BeO 0.01 0.03 Na2O 0.03 0.10 CaO 0.02 0.07 P2O5 0.05 0.17 TFe2O3 0.01 0.03 SiO2 0.20 0.66 K2O 0.02 0.07 TiO2 0.003 0.01 MgO 0.01 0.03
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表 3 铍及主量元素测定结果精密度统计
Table 3. Precision statistics of determination results for beryllium and major elements
样品编号 项目 Al2O3 BeO CaO TFe2O3 K2O MgO MnO Na2O SiO2 TiO2 GBW07151 含量平均值(%) 14.77 0.36 0.58 0.58 3.85 0.070 0.036 4.65 73.91 0.016 RSD (%) 0.52 1.31 3.86 3.80 2.02 3.16 3.38 0.93 0.51 6.83 YC (%) 2.57 5.82 7.73 7.73 4.46 12.45 14.21 4.18 0.46 16.57 Lz-2
(实际铍矿石样品)含量平均值(%) 17.53 10.52 0.15 0.74 0.20 0.068 0.12 2.18 66.09 0.032 RSD (%) 0.62 1.59 6.14 3.67 3.89 1.85 3.02 2.22 0.61 6.82 YC (%) 2.35 2.02 10.60 7.27 9.95 12.52 11.12 5.36 0.54 14.54
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表 4 标准物质中铍及主量元素的测定值与标准值对比
Table 4. Comparison of determination values and standard values of beryllium and major elements in standard materials
样品编号 测定参数 Al2O3 BeO CaO TFe2O3 K2O MgO MnO Na2O SiO2 TiO2 GBW07150 测定值(%) 14.93 0.06 0.60 0.49 4.14 0.07 0.03 4.75 73.74 0.01 标准值(%) 14.86 0.060 0.582 0.513 4.10 0.071 0.03 4.79 73.97 0.015 相对误差(%) 0.47 −1.67 3.26 −3.70 0.98 −4.23 0.00 −0.84 −0.31 −6.67 YB (%) 1.81 6.08 5.46 5.64 3.09 8.78 10.41 2.92 0.32 11.85 GBW07151 测定值(%) 14.74 0.35 0.61 0.57 3.94 0.08 0.04 4.74 74.04 0.02 标准值(%) 14.81 0.365 0.584 0.593 3.89 0.069 0.036 4.67 73.99 0.016 相对误差(%) −0.47 −3.29 4.62 −3.88 1.29 8.70 −2.78 1.50 0.07 0.00 YB (%) 1.81 4.10 5.46 5.44 3.14 8.83 10.05 2.95 0.32 11.71 GBW07183 测定值(%) 15.74 2.99 0.51 0.46 3.17 0.08 0.02 3.64 71.84 0.01 标准值(%) 15.55 3.02 0.52 0.47 3.28 0.083 0.02 3.67 71.97 0.01 相对误差(%) 1.22 −0.99 −1.92 −2.13 −3.26 −2.41 5.00 −0.82 −0.18 0.00 YB (%) 1.77 2.29 5.62 5.76 3.33 8.50 11.24 3.21 0.34 12.76
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表 5 碱熔法和酸溶法处理样品铍及主量元素测定结果比对
Table 5. Comparison of determination results for beryllium and major elements in samples processed using alkaline fusion and acid dissolution
样品编号 测定参数 Al2O3 BeO CaO TFe2O3 K2O MgO MnO Na2O TiO2 Be-xh 碱熔法测定值(%) 16.97 0.14 20.99 11.55 1.33 1.21 1.61 1.34 − 酸溶法测定值(%) 17.27 0.11 21.20 11.37 1.27 1.17 1.64 1.24 − RD (%) −1.72 19.56 −1.00 1.50 4.65 3.28 −2.33 7.52 − Be-rgl 碱熔法测定值(%) 0.68 12.81 1.77 26.10 0.08 0.29 16.47 − 0.026 酸溶法测定值(%) 0.66 13.05 1.90 26.46 0.08 0.31 16.73 − 0.021 RD (%) 2.78 −1.85 −7.24 −1.34 −4.57 −7.40 −1.55 − 21.28 Lz-2 碱熔法测定值(%) 17.44 10.62 0.15 0.71 0.24 0.068 0.11 2.11 0.033 酸溶法测定值(%) 17.38 10.55 0.13 0.71 0.26 0.066 0.12 2.29 0.029 RD (%) 0.35 0.67 17.05 −0.06 −6.27 2.48 −2.53 −8.21 12.90 Be-kq 碱熔法测定值(%) 19.77 0.54 0.88 0.89 4.17 0.041 0.22 2.93 0.010 酸溶法测定值(%) 19.59 0.49 0.92 0.92 4.27 0.038 0.23 3.10 − RD (%) 0.90 8.48 −3.54 −3.18 −2.35 6.73 −3.51 −5.68 − 注：表格中的“−” 为低于本方法测定下限的测定结果。
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