Determination of Boron, Iodine, Tin and Germanium in Geochemical Samples by Inductively Coupled Plasma-Mass Spectrometry
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摘要: 在多目标的配套方法中,硼、碘、锡、锗四个元素的分析涉及三个配套方法,发射光谱法测定硼、锡,原子荧光光谱法测定锗,分光光度法或电感耦合等离子体质谱法(ICP-MS)测定碘,分析成本高、检测效率低。本文建立了一种ICP-MS同时测定地球化学样品中硼、碘、锡、锗的方法。样品用过氧化钠熔矿,使难熔元素锡分解完全,熔盐经水提取后加入铼内标,再用阳离子交换树脂分离大量钠盐及大部分阳离子,保证了盐分满足质谱测定的要求。方法检出限分别为硼0.92μg/g、碘0.10μg/g、锡0.29μg/g、锗0.09μg/g,满足多目标测试要求。用国家一级标准物质验证,测定值与认定值一致,相对标准偏差(RSD,n=12)≤ 5%,适用于批量地球化学样品中硼、碘、锡、锗的测定,样品处理过程简便,检测效率高。Abstract:
BACKGROUNDIn the multi-objective method, the analysis of four elements of boron, iodine, tin and germanium involves three supporting methods. Boron and tin were determined by Emission Spectrometry, germanium was determined by Atomic Fluorescence Spectrometry, and iodine was determined by Spectrophotometry or Inductively Coupled Plasma-Mass Spectrometry. The analysis cost is high and the detection efficiency is low. OBJECTIVESTo establish an easy, highly efficient and precise, low-cost method for determination of boron, iodine, tin and germanium in geochemical samples by Inductively Coupled Plasma-Mass Spectrometry. METHODSThe sample is fused with sodium peroxide to completely decompose the refractory element tin. The molten salt is extracted by water and the internal standard is added, and then the cation exchange resin is used to separate a large amount of sodium salt and most of the cations, ensuring that the salt meets the requirements of mass spectrometry analysis. RESULTSThe element detection limits were 0.92μg/g, 0.10μg/g, 0.29μg/g, 0.09μg/g for boron, iodine, tin and germanium, respectively. The relative standard deviation (RSD, n=12) was smaller than 5%. The method was verified by certified reference materials, and the measured values were consistent with the certified values. CONCLUSIONSThe method is suitable for the determination of boron, iodine, tin and germanium in batch geochemical samples. -
Key words:
- alkali fusion /
- cation resin separation /
- Inductively Coupled Plasma-Mass Spectrometry /
- boron /
- iodine /
- tin /
- germanium
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表 1 硼、碘、锡、锗混合标准母液的配制
Table 1. Mixed standard solution of boron, iodine, tin, germanium
元素 标准系列(ng/mL) S0 S1 S2 S3 S4 S5 S6 S7 B 0.0 20.0 40.0 100.0 200.0 400.0 600.0 2000.0 I 0.0 2.0 4.0 10.0 20.0 40.0 60.0 200.0 Sn 0.0 4.0 8.0 20.0 40.0 80.0 120.0 400.0 Ge 0.0 2.0 4.0 10.0 20.0 40.0 60.0 100.0 表 2 不同内标加入方式对标样GBW07401的测定效果
Table 2. Effect of different ways of internal standard addition in reference material GBW07401
元素 内标加入
方式测定结果(μg/g) 相对标准
偏差(%)B 在线内标 47.1 49.3 50.4 46.1 52.4 54.6 48.1 51.1 53.3 55.8 46.3 47.1 6.65 预先加入 50.1 49.8 51.6 52.1 49.3 50.6 51.3 48.9 49.3 52.3 50.8 49.6 2.29 I 在线内标 1.65 2.14 1.86 1.71 1.98 1.65 1.74 1.85 1.93 2.02 1.96 1.64 9.01 预先加入 1.74 1.88 1.91 1.83 1.69 1.74 1.89 1.86 1.72 1.77 1.81 1.78 4.04 Sn 在线内标 5.56 5.76 6.98 6.93 5.62 5.84 6.45 6.71 6.87 6.82 5.65 5.57 9.75 预先加入 5.71 5.86 6.41 5.69 5.94 6.11 6.34 5.87 6.03 5.98 6.17 6.34 4.01 Ge 在线内标 1.26 1.44 1.37 1.18 1.19 1.43 1.41 1.45 1.48 1.15 1.21 1.39 9.19 预先加入 1.36 1.29 1.31 1.39 1.26 1.29 1.35 1.24 1.37 1.25 1.28 1.39 4.16 表 3 精密度实验
Table 3. Precision tests of the method
标准物质
编号元素 12次测定结果
(μg/g)平均值
(μg/g)相对标准
偏差(%)GBW07401 B 52.6 48.9 48.49 49.07 51.08 48.99 50.17 49.09 4849.04 49.59 47.69 49.39 2.59 I 1.805 1.808 1.729 1.963 1.856 1.868 1.772 1.999 1.767 1.917 1.847 1.868 1.850 4.29 Sn 6.112 6.320 6.375 6.458 6.033 6.521 6.179 6.220 6.094 6.058 6.007 6.161 6.212 2.74 Ge 1.342 1.377 1.314 1.327 1.374 1.345 1.405 1.303 1.311 1.353 1.326 1.358 1.345 2.27 GBW07404 B 97.88 95.67 96.61 97.44 97.42 95.8 97.77 98.53 93.82 95.25 95.01 98.46 96.64 1.49 I 8.819 9.473 9.014 10.27 9.369 9.392 8.865 8.758 8.487 9.36 8.749 8.908 9.122 4.88 Sn 5.722 5.558 5.549 5.689 5.701 5.980 5.793 5.500 5.701 5.884 5.976 6.051 5.759 3.15 Ge 1.914 1.889 1.911 1.860 1.958 1.836 2.083 1.846 1.861 1.869 1.957 1.856 1.903 3.66 GBW07454 B 53.78 51.41 51.7 53.1 53.6 53.05 51.59 52.37 53.31 53.01 50.58 51.71 52.43 1.80 I 1.45 1.548 1.542 1.646 1.647 1.741 1.61 1.505 1.641 1.62 1.556 1.563 1.59 4.94 Sn 2.931 2.862 2.911 2.835 2.904 2.843 2.950 2.833 2.941 2.857 2.884 2.835 2.882 1.52 Ge 1.316 1.427 1.415 1.340 1.476 1.320 1.307 1.311 1.366 1.444 1.319 1.405 1.371 4.38 表 4 准确度实验
Table 4. Accuracy tests of the method
标准物质
编号B I Sn Ge 认定值
(μg/g)测定值
(μg/g)相对误差
(%)认定值
(μg/g)测定值
(μg/g)相对误差
(%)认定值
(μg/g)测定值
(μg/g)相对误差
(%)认定值
(μg/g)测定值
(μg/g)相对误差
(%)GBW07401 50 49.4 -1.2 1.34 1.32 -1.49 6.1 6.9 8.2 1.8 1.85 2.78 GBW07402 36 35.8 -0.56 1.2 1.23 2.5 3 3.14 4.67 1.8 1.95 8.33 GBW07403 23 24 4.35 1.16 1.1 -5.17 2.5 2.71 8.4 1.3 1.32 1.54 GBW07404 97 99.6 2.68 1.9 1.88 -1.05 5.7 5.75 0.88 9.4 8.83 -6.06 GBW07405 53 51.9 -2.08 2.6 2.65 1.92 18 16.4 -8.89 3.8 3.87 1.84 GBW07406 57 56.1 -1.58 3.2 3.16 1.25 72 67.5 -6.25 19.4 19.4 0 GBW07407 10 11.5 15 1.6 1.73 8.12 3.6 3.36 -6.67 19 18.3 -3.68 GBW07408 54 54.7 1.3 1.27 1.19 -6.3 2.8 2.64 -5.71 1.7 1.84 8.24 GBW07454 54 54.5 0.93 1.31 1.23 -6.11 2.9 3 3.45 1.5 1.6 6.67 GBW07455 52 51 -1.92 1.3 1.4 7.69 2.8 2.64 -5.71 1.1 1.12 1.82 GBW07456 64 64.5 0.78 1.47 1.42 -3.4 4 3.92 -2 1 1.1 10 GBW07457 80 74.5 -6.88 1.83 1.92 4.92 8.7 9.21 5.86 1.2 1.3 8.33 -
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