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封闭压力酸溶-电感耦合等离子体质谱法同时测定电气石中29种元素

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成学海, 夏传波, 郑建业, 张文娟, 刘晶. 封闭压力酸溶-电感耦合等离子体质谱法同时测定电气石中29种元素[J]. 岩矿测试, 2017, 36(3): 231-238. doi: 10.15898/j.cnki.11-2131/td.201609220143
引用本文: 成学海, 夏传波, 郑建业, 张文娟, 刘晶. 封闭压力酸溶-电感耦合等离子体质谱法同时测定电气石中29种元素[J]. 岩矿测试, 2017, 36(3): 231-238. doi: 10.15898/j.cnki.11-2131/td.201609220143
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Xue-hai CHENG, Chuan-bo XIA, Jian-ye ZHENG, Wen-juan ZHANG, Jing LIU. Simultaneous Determination of 29 Trace Elements in Tourmaline by Inductively Coupled Plasma-Mass Spectrometry with Sealed Press Acid Decomposition[J]. Rock and Mineral Analysis, 2017, 36(3): 231-238. doi: 10.15898/j.cnki.11-2131/td.201609220143
Citation: Xue-hai CHENG, Chuan-bo XIA, Jian-ye ZHENG, Wen-juan ZHANG, Jing LIU. Simultaneous Determination of 29 Trace Elements in Tourmaline by Inductively Coupled Plasma-Mass Spectrometry with Sealed Press Acid Decomposition[J]. Rock and Mineral Analysis, 2017, 36(3): 231-238. doi: 10.15898/j.cnki.11-2131/td.201609220143
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封闭压力酸溶-电感耦合等离子体质谱法同时测定电气石中29种元素

  • 1.

    山东省地质科学研究院, 山东 济南 250013

  • 2.

    山东省金属矿产成矿地质过程与资源利用重点实验室, 山东 济南 250013

  • 基金项目:
    国土资源公益性行业科研专项（201311096-03）
详细信息
    作者简介: 成学海, 高级工程师, 主要从事岩矿测试分析工作。E-mail:chengxuehai2009@sohu.com

  • 中图分类号: P578.953;O657.63

Simultaneous Determination of 29 Trace Elements in Tourmaline by Inductively Coupled Plasma-Mass Spectrometry with Sealed Press Acid Decomposition

  • 1.

    Shandong Institute of Geological Sciences, Jinan 250013, China

  • 2.

    Key Laboratory of Geological Processes for Mineralization of Metal Minerals and Resource Utilization in Shandong Province, Jinan 250013, China

    摘要
  • 电气石是一种含硼的铝硅酸盐矿物，是重要的非金属矿产资源和成岩成矿作用的灵敏示踪剂，因类质同象置换普遍使其组成成分多变，主量元素为Si、B、Al、Fe和Mg，微量元素有稀土元素、Cu、Pb、Zn、Sn、Ag和Sr等。电气石的化学性质非常稳定，不能被一般的酸或碱完全溶解，本文采用硝酸-氢氟酸封闭压力溶矿，50%王水封闭压力复溶进行样品前处理，建立了电感耦合等离子体质谱法测定电气石中稀有轻金属、重金属、放射性金属、稀土元素等29种元素的分析方法。方法检出限为0.003~0.4 μg/g，精密度（RSD，n=12）为0.9%~9.2%；国家标准物质的测定值与标准值基本相符，各元素的加标回收率为95%~105%。本方法解决了电气石样品难分解、复溶时易出现氢氧化铝微细残渣的问题，样品试液中B、Al、Fe等主要共存离子的干扰小，各待测元素测定结果准确、可靠。
    Tourmaline is a boron-containing aluminosilicate mineral, which is an important non-metallic mineral resource, and an indicator for rock-forming and ore-forming processes. The chemical composition of tourmaline is highly variable due to the isomorphic substitution. The major elements of tourmaline are Si, Al, B, Fe and Mg, whereas the trace elements are rare earth (REE), Cu, Pb, Zn, Sn, Ag and Sr. The stable chemical properties make it difficult to complete digestion by acid or alkaline reagents. Samples were digested by HNO3-HF in a sealed and pressurized device. 50% aqua regia was used to repeat dissolution. Twenty nine trace elements in tourmaline including precious light metals, heavy metals, radioactive metals and rare earth elements were determined by Inductively Coupled Plasma-Mass Spectrometry. The detection limits (n=12) ranged from 0.003 to 0.4 μg/g and the relative standard deviations (RSD, n=12) ranged from 0.9% to 9.17%. The proposed method was applied to the determination of certified reference materials and the results were consistent with the certified values. The recoveries of elements ranged from 90% to 110%. This method solves the problem for difficult dissolution of the tourmaline sample and the fine residue of aluminum hydroxide in the redissolution process. The coexisted ions B, Al and Fe in sample solutions show only slight interference, and the measurement results are accurate and reliable.
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  • 图 1  不同的复溶方法比较

    Figure 1. 

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    表 1  三种样品分解方法的分析结果比较

    Table 1.  omparison of the analytical results with three digestion methods

    元素 样品DQS-1 样品DQS-4 样品DQS-6
    敞开酸溶
    (μg/g)    		 封闭压力酸溶
    (μg/g)    		 碱熔
    (μg/g)    		 敞开酸溶
    (μg/g)    		 封闭压力酸溶
    (μg/g)    		 碱熔
    (μg/g)    		 敞开酸溶
    (μg/g)    		 封闭压力酸溶
    (μg/g)    		 碱熔
    (μg/g)
    Li 9.32 12.1 12.3 3.82 6.14 6.08 3583 8000 7889
    Rb 13.2 14.1 13.6 5.43 5.71 5.47 772 803 819
    Cs 7.73 8.17 8.42 0.29 0.32 0.34 396 415 408
    Co 12.6 18.8 19.4 15.6 24.3 25.7 0.41 0.45 0.42
    Cr 304 846 863 92.1 158 168 2.52 3.61 3.75
    Cd 0.024 0.041 0.045 0.055 0.093 0.096 0.45 0.92 0.97
    Ni 66.3 107 114 38.7 53.3 51.2 1.65 2.38 2.46
    Cu 3.54 5.21 5.60 4.54 6.21 6.38 1.15 1.85 1.76
    Pb 3.63 4.71 4.59 13.8 15.1 14.6 44.2 75.9 73.9
    Zn 25.6 30.6 31.3 126 132 139 3.75 4.12 4.19
    Sr 75.6 102 98.7 793 1138 1073 64.9 81.3 83.5
    Th 1.75 2.84 2.55 0.75 0.91 0.97 1.62 1.81 2.02
    U 2.17 2.65 2.57 0.53 0.79 0.81 1.58 1.79 1.71
    Sc 36.2 56.3 59.1 17.4 20.4 21.2 2.13 2.45 2.31
    Y 25.9 30.9 29.1 7.93 9.45 9.32 1.15 1.42 1.58
    La 11.5 15.1 14.6 8.55 9.17 9.31 0.49 0.53 0.49
    Ce 25.1 28.3 27.1 16.4 18.7 17.1 0.53 0.64 0.65
    Pr 3.13 3.60 3.47 2.25 2.69 2.52 0.081 0.095 0.098
    Nd 11.7 12.8 13.3 9.5 10.6 11.2 0.20 0.35 0.39
    Sm 2.60 3.61 3.82 1.83 2.13 2.28 0.12 0.15 0.14
    Eu 0.31 0.46 0.44 0.38 0.65 0.63 0.009 0.012 0.011
    Gd 2.92 4.27 4.12 1.56 2.09 1.92 0.043 0.053 0.050
    Tb 0.46 0.84 0.79 0.21 0.26 0.28 0.011 0.014 0.012
    Dy 4.12 5.12 5.27 1.2 1.44 1.56 0.043 0.059 0.052
    Ho 0.91 1.19 1.11 0.21 0.35 0.34 0.011 0.013 0.014
    Er 2.36 3.30 3.44 0.63 0.85 0.89 0.021 0.032 0.031
    Tm 0.36 0.52 0.51 0.093 0.13 0.12 0.0032 0.0051 0.0048
    Yb 3.18 3.41 3.57 0.63 0.77 0.79 0.022 0.035 0.039
    Lu 0.47 0.57 0.54 0.10 0.13 0.11 0.0031 0.0045 0.0052
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    表 2  方法精密度及准确度

    Table 2.  Precision and accuracy tests of the methods

    元素 GBW07404 GBW07107
    测定平均值
    (μg/g)    		 标准值
    (μg/g)    		 标准偏差
    (μg/g)    		 RSD
    (%)    		 相对误差
    (%)    		 测定平均值
    (μg/g)    		 标准值
    (μg/g)    		 标准偏差
    (μg/g)    		 RSD
    (%)    		 相对误差
    (%)
    Li 56.4 55 2.03 3.6 2.6 44.8 44 1.84 4.1 1.8
    Rb 73.9 75 2.59 3.5 -1.5 209.2 205 8.79 4.2 2.0
    Cs 20.9 21.4 0.86 4.1 -2.3 14.5 14 0.46 3.2 3.5
    Co 21.5 22 0.19 0.9 -2.3 20.6 21 0.31 1.5 -1.9
    Ni 65.5 64 2.36 3.6 2.3 38.2 37 0.96 2.5 3.3
    Cu 42 40 1.93 4.6 5.0 41.1 40 2.67 6.5 2.6
    Zn 212.8 210 3.83 1.8 1.3 54.5 55 2.45 4.5 -1.0
    Sr 76 77 1.22 1.6 -1.4 89.5 90 2.77 3.1 -0.6
    Cd 0.36 0.35 0.033 9.2 2.9 0.031 0.033 0.00 4.8 -4.8
    Cr 367 370 5.51 1.5 -0.8 103.7 99 1.24 1.2 4.7
    Pb 60.3 58 1.75 2.9 3.9 8.5 8.7 0.42 4.9 -2.4
    Th 28.1 27 0.90 3.2 4.2 13.3 12.8 0.64 4.8 3.8
    U 6.5 6.7 0.27 4.2 -2.7 1.6 1.5 0.04 2.7 5.0
    Sc 18.5 20 1.50 8.1 -7.5 19.1 18.5 0.50 2.6 3.2
    Y 38.4 39 0.84 2.2 -1.5 26.6 26 0.93 3.5 2.2
    La 54 53 1.51 2.8 2.0 59.9 62 2.28 3.8 -3.4
    Ce 139.3 136 4.74 3.4 2.4 111.7 109 3.46 3.1 2.5
    Pr 8.2 8.4 0.25 3.1 -2.9 13.1 13.6 0.54 4.1 -3.6
    Nd 26.2 27 0.84 3.2 -2.9 49.5 48 1.73 3.5 3.1
    Sm 4.6 4.4 0.21 4.5 3.4 8.3 8.4 0.34 4.1 -1.6
    Eu 0.86 0.85 0.02 2.3 1.3 1.8 1.7 0.03 1.9 4.9
    Gd 4.6 4.7 0.21 4.6 -2.0 6.8 6.7 0.44 6.5 1.6
    Tb 0.96 0.94 0.05 5.5 1.9 0.97 1.02 0.02 2.1 -4.7
    Dy 6.7 6.6 0.15 2.3 1.1 5.3 5.1 0.15 2.9 3.3
    Ho 1.5 1.46 0.10 6.5 1.3 0.95 0.98 0.02 2.1 -2.8
    Er 4.4 4.5 0.22 5.1 -2.2 2.8 2.7 0.17 5.9 4.0
    Tm 0.72 0.7 0.02 2.8 3.0 0.41 0.43 0.03 6.9 -4.3
    Yb 4.6 4.8 0.19 4.1 -3.8 2.5 2.6 0.05 2.1 -4.8
    Lu 0.73 0.75 0.04 6.1 -2.6 0.40 0.41 0.03 6.6 -3.7
    下载: 导出CSV

    表 3  样品比对实验

    Table 3.  Comparison of analytical results in different laboratories

    元素 样品DQS-1(μg/g) 样品DQS-4(μg/g) 样品DQS-6(μg/g)
    本文 中南 沈阳 郑州 本文 中南 沈阳 郑州 本文 中南 沈阳 郑州
    Li 12.1 13.1 12.2 12.6 6.14 6.05 5.95 6.45 8000 7800 7841 7730
    Rb 14.1 13.6 14.5 13.3 5.71 5.53 5.68 5.62 803 804 817 807
    Cs 8.17 8.51 8.45 8.43 0.32 0.27 0.28 0.25 415 410 409 400
    Co 18.8 20.1 18.6 19.3 24.3 24.1 23.1 22.3 0.45 0.46 0.47 0.48
    Cr 846 856 868 885 158 165 169 172 3.61 3.54 4.32 4.45
    Cd 0.041 0.040 0.041 0.047 0.093 0.090 0.11 0.13 0.92 0.93 0.96 0.95
    Ni 107 113 109 111 53.3 50.8 51.9 52.3 2.38 1.95 2.40 2.45
    Cu 5.21 5.02 5.05 5.10 6.21 6.08 6.25 6.23 1.85 1.17 2.05 2.11
    Pb 4.71 4.25 4.65 5.11 15.1 14.1 15.2 14.55 75.9 74.3 77.8 80.1
    Zn 30.6 30.7 30.2 30.3 132 141 133 142 4.12 5.88 3.98 4.11
    Sr 102 96.2 94.7 95.4 1138 1040 1050 1044 81.3 82.3 81.5 84.4
    Th 2.84 2.56 2.75 2.56 0.91 0.97 0.99 0.96 1.81 1.94 1.96 1.98
    U 2.65 2.38 2.43 2.41 0.79 0.75 0.84 0.75 1.79 1.67 1.70 1.53
    Sc 56.3 54.2 59.2 60.8 20.4 21.9 20.2 20.1 2.45 2.01 1.98 1.86
    Y 30.9 30.8 30.1 28.1 9.45 9.21 9.15 9.21 1.42 1.46 1.60 1.47
    La 15.1 14.2 14.1 13.9 9.17 9.11 9.01 9.02 0.53 0.51 0.49 0.46
    Ce 28.3 28.4 27.6 26.8 18.7 19.4 17.2 16.8 0.64 0.70 0.72 0.74
    Pr 3.60 3.45 3.55 3.73 2.69 2.63 2.62 2.91 0.095 0.10 0.10 0.11
    Nd 12.8 13.6 13.8 13.5 10.6 10.9 10.8 10.4 0.35 0.32 0.36 0.37
    Sm 3.61 3.89 3.45 3.33 2.13 2.26 2.31 2.28 0.15 0.14 0.15 0.15
    Eu 0.46 0.47 0.42 0.40 0.65 0.65 0.62 0.61 0.012 0.017 0.017 0.020
    Gd 4.27 4.23 4.10 4.13 2.09 1.99 1.91 1.65 0.053 0.070 0.052 0.053
    Tb 0.84 0.81 0.80 0.73 0.26 0.30 0.29 0.26 0.014 0.010 0.010 0.009
    Dy 5.12 5.35 5.22 5.15 1.44 1.59 1.46 1.31 0.059 0.059 0.053 0.050
    Ho 1.19 1.17 1.12 1.11 0.35 0.30 0.29 0.28 0.013 0.014 0.010 0.010
    Er 3.30 3.29 3.21 2.99 0.85 0.86 0.82 0.76 0.032 0.027 0.028 0.032
    Tm 0.52 0.52 0.54 0.52 0.13 0.13 0.13 0.12 0.0051 0.006 0.004 0.005
    Yb 3.41 3.45 3.43 3.32 0.77 0.80 0.81 0.78 0.035 0.04 0.03 0.03
    Lu 0.57 0.54 0.57 0.51 0.13 0.13 0.14 0.12 0.0045 0.005 0.006 0.006
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收稿日期:  2016-09-22
修回日期:  2017-05-20
录用日期:  2017-05-28

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