中国地质学会岩矿测试技术专业委员会、国家地质实验测试中心主办

氟化氢铵快速分解-电感耦合等离子体质谱法测定含刚玉铝土矿中锂镓锆稀土等痕量元素

刘贵磊, 许春雪, 陈宗定, 温宏利. 氟化氢铵快速分解-电感耦合等离子体质谱法测定含刚玉铝土矿中锂镓锆稀土等痕量元素[J]. 岩矿测试, 2020, 39(5): 670-681. doi: 10.15898/j.cnki.11-2131/td.202003120031
引用本文: 刘贵磊, 许春雪, 陈宗定, 温宏利. 氟化氢铵快速分解-电感耦合等离子体质谱法测定含刚玉铝土矿中锂镓锆稀土等痕量元素[J]. 岩矿测试, 2020, 39(5): 670-681. doi: 10.15898/j.cnki.11-2131/td.202003120031
Gui-lei LIU, Chun-xue XU, Zong-ding CHEN, Hong-li WEN. Determination of Lithium, Gallium, Zirconium, Rare Earth Elements and Other Trace Elements in Corundum-bearing Bauxite by Inductively Coupled Plasma-Mass Spectrometry with Rapid Decomposition of Ammonium Bifluoride[J]. Rock and Mineral Analysis, 2020, 39(5): 670-681. doi: 10.15898/j.cnki.11-2131/td.202003120031
Citation: Gui-lei LIU, Chun-xue XU, Zong-ding CHEN, Hong-li WEN. Determination of Lithium, Gallium, Zirconium, Rare Earth Elements and Other Trace Elements in Corundum-bearing Bauxite by Inductively Coupled Plasma-Mass Spectrometry with Rapid Decomposition of Ammonium Bifluoride[J]. Rock and Mineral Analysis, 2020, 39(5): 670-681. doi: 10.15898/j.cnki.11-2131/td.202003120031

氟化氢铵快速分解-电感耦合等离子体质谱法测定含刚玉铝土矿中锂镓锆稀土等痕量元素

  • 基金项目:
    中国地质调查局地质调查项目(DD20190323,DD20190475);国家自然科学基金项目(21601041)
详细信息
    作者简介: 刘贵磊, 博士, 助理研究员, 主要从事岩矿测试分析和标准化工作。E-mail:liuguilei2008@163.com
  • 中图分类号: P578.496;O657.63

Determination of Lithium, Gallium, Zirconium, Rare Earth Elements and Other Trace Elements in Corundum-bearing Bauxite by Inductively Coupled Plasma-Mass Spectrometry with Rapid Decomposition of Ammonium Bifluoride

  • 铝土矿中常伴有锂、镓、锆、稀土等有用组分,完全提取并准确测定其含量对于铝土矿资源综合评价和综合利用具有重要意义。然而铝土矿中常常含有少量刚玉,常规的四酸、五酸和封闭压力酸溶法对其分解不完全,导致测定结果偏低。本文采用氟化氢铵作熔剂,高温下在旋盖PFA小瓶中分解样品,通过在熔样过程中使用少量硫酸,对不同熔矿温度、消解时间及试剂用量等因素详细考察,确定了最佳熔矿条件[200℃,3h,试样比4:1(称样量50mg)],建立了氟化氢铵分解-电感耦合等离子体质谱法测定含刚玉铝土矿中37种痕量元素的分析方法。本方法能快速、有效地分解含刚玉铝土矿,经三种铝土矿国家标准物质GBW07177、GBW07181和GBW07182验证,并与四酸、五酸和封闭压力酸溶法的测定结果对比,三种标准物质中Li、Ga、Sr、Zr、Pb等9种元素的回收率分别在95.0%~115.0%、90.0%~110.0%和90.0%~110.0%之间,测定值与认定值相符。同时,本方法实现了铝土矿(Al2O3含量在42.97%~90.36%之间)中Al、Ti、P等主量元素的精确分析,进一步验证了其用来测定铝土矿中痕量元素的准确性。方法检出限为0.002~0.43μg/g,与传统硝酸-氢氟酸密闭消解法的检出限(0.000~0.48μg/g)基本相当,精密度在1.14%~8.84%之间,能够满足铝土矿中痕量元素的分析要求。
  • 加载中
  • 图 1  不同熔矿温度下铝土矿标准物质(GBW07177、GBW07178、GBW07181)中Li、Ga、Sr、Zr的回收率

    Figure 1. 

    图 2  不同消解时间下铝土矿标准物质(GBW07177、GBW07178、GBW07181)中Li、Ga、Sr、Zr的回收率

    Figure 2. 

    图 3  氟化氢铵分解50~200mg铝土矿标准物质(GBW07177)时11种元素的回收率

    Figure 3. 

    图 4  不同熔矿方法下铝土矿标准物质(GBW07177、GBW07181、GBW07182)中9种元素的回收率

    Figure 4. 

    图 5  氟化氢铵分解铝土矿标准物质(GBW07177~GBW07182)中Al、Ti、P的回收率

    Figure 5. 

    表 1  四种溶(熔)矿方法下铝土矿标准物质(GBW07177、GBW07181、GBW07182)中37种痕量元素的ICP-MS分析结果

    Table 1.  ICP-MS analytical results for determination of 37 trace elements in bauxite standard materials (GBW07177, GBW07181, GBW07182) by four sample dissolution (melting) methods

    待测
    元素
    认定值(μg/g) 方法一(μg/g) 方法二(μg/g) 方法三(μg/g) 方法四(μg/g)
    GBW
    07177
    GBW
    07181
    GBW
    07182
    GBW
    07177
    GBW
    07181
    GBW
    07182
    GBW
    07177
    GBW
    07181
    GBW
    07182
    GBW
    07177
    GBW
    07181
    GBW
    07182
    GBW
    07177
    GBW
    07181
    GBW
    07182
    Li 80.6±5.5 35.1±4 147±12 51.3 27.5 120 79.3 36.8 151 82.6 33.6 140 90.2 39.0 162
    Be / / / 7.20 5.43 5.18 3.78 3.81 3.71 4.25 3.33 3.60 8.86 6.83 5.52
    Sc / / / 6.82 4.05 5.85 50.3 45.2 44.8 51.5 42.1 42.3 62.5 48.7 46.6
    V 198±27 210±26 216±27 194 208 232 78.3 85.4 201 92.5 156 191 206 222 220
    Cr 215±7 267±20 233±17 113 147 124 75.5 40.3 75.8 86.2 41.0 74.9 231 264 223
    Co / / / 5.32 0.44 1.70 5.46 0.65 2.27 5.35 0.68 2.19 6.09 1.08 2.25
    Ni / / / 31.1 6.0 22.4 23.4 2.1 19.6 26.3 3.9 21.6 36.3 9.0 23.3
    Cu 30.6±3.3 19.5±3.8 24.8±2.4 33.9 19.0 22.8 26.0 9.8 21.6 28.1 16.6 20.0 31.8 17.6 22.7
    Zn 24±1.9 7.4±1.2 17.7±3.3 24.5 6.9 16.5 24.9 7.0 18.5 24.5 7.9 17.0 25.9 7.9 19.3
    Ga 70±8 82±15 72±11 40.2 35.6 31.2 19.2 21.3 30.5 22.2 20.1 30.5 72.3 87.0 69.9
    Rb / / / 7.27 1.70 6.27 7.31 1.64 6.24 7.26 1.60 6.14 7.94 1.86 6.02
    Sr 691±44 345±12 292±17 177 80 71 712 337 304 704 327 301 714 349 279
    Y / / / 20.5 15.0 14.2 85.5 62.2 61.4 88.5 61.7 63.3 90.0 56.4 60.4
    Zr 886±95 1160±110 986±84 838 1189 995 648 870 893 692 1056 927 914 1303 993
    Nb / / / 64.1 39.6 46.5 16.9 4.3 75.7 83.7 91.3 80.6 88.2 96.7 80.4
    Cs / / / 0.37 0.08 0.48 0.31 0.07 0.43 0.33 0.06 0.39 0.38 0.08 0.48
    Ba / / / 16.9 7.2 10.8 65.4 35.1 47.6 71.2 35.9 46.0 77.5 43.0 51.6
    La / / / 93.1 75.5 72.2 259 129 149 260 130 147 259 120 151
    Ce / / / 223 111 116 484 253 299 523 255 296 518 247 294
    Pr / / / 18.2 11.8 12.5 58.4 21.8 28.6 62.6 22.5 28.8 64.6 22.7 30.5
    Nd / / / 63.7 34.3 39.3 218 66 95 233 69.7 95.7 249 76.6 111
    Sm / / / 9.94 4.92 5.89 37.3 11.2 15.8 39.5 11.6 16.2 40.1 11.3 16.7
    Eu / / / 1.62 0.84 0.98 6.34 2.00 2.86 6.59 2.14 2.94 7.75 2.05 2.96
    Gd / / / 6.18 3.11 3.49 22.2 7.93 10.4 23.8 7.77 10.2 29.3 7.77 10.8
    Tb / / / 0.84 0.54 0.54 3.19 1.58 1.79 3.35 1.64 1.81 4.11 1.64 1.79
    Dy / / / 4.66 3.47 3.15 18.5 11.0 11.8 19.6 11.6 12.1 23.7 11.8 12.6
    Ho / / / 0.89 0.68 0.59 3.52 2.35 2.42 3.78 2.49 2.47 4.07 2.33 2.46
    Er / / / 2.46 1.85 1.68 9.71 7.15 7.16 10.6 7.45 7.52 12.3 7.45 7.54
    Tm / / / 0.37 0.28 0.26 1.51 1.13 1.14 1.61 1.22 1.21 1.88 1.21 1.23
    Yb / / / 2.64 1.75 1.65 10.7 8.12 8.10 11.4 8.59 8.41 13.1 8.61 8.45
    Lu / / / 0.38 0.25 0.25 1.54 1.23 1.21 1.66 1.28 1.30 1.84 1.26 1.31
    Hf / / / 25.3 35.7 29.9 20.4 28.1 28.3 22.9 36.1 30.9 29.5 42.9 32.6
    Ta / / / 2.22 0.67 2.01 0.79 0.33 3.30 6.99 6.88 7.19 8.18 9.78 7.68
    Tl / / / 0.06 0.01 0.03 0.06 0.01 0.04 0.06 0.01 0.04 0.07 0.01 0.03
    Pb 116±9 26.7±5.7 35.7±6.9 75.7 10.4 16.1 94.2 21.3 25.5 99.7 22.2 26.3 115 26.0 32.1
    Th / / / 64.9 66.4 48.8 92.4 99.2 85.5 99.9 101 90.0 109 99.5 88.9
    U / / / 37.5 35.8 30.0 32.9 32.4 27.9 35.4 34.3 29.6 37.0 34.3 26.9
    注:“/”表示该标准物质没有提供此元素的定值。
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    表 2  氟化氢铵分解和传统硝酸-氢氟酸密闭消解法的过程空白和检出限

    Table 2.  Process blanks and detection limits for NH4HF2 decomposition and conventional HF-HNO3 closed digestion

    待测
    元素
    分析质量
    (丰度,%)
    过程空白(ng/g, n=12) 检出限(μg/g)
    1mL氢氟酸
    1mL硝酸
    分析纯
    氟化氢铵
    优级纯
    氟化氢铵
    1mL氢氟酸-
    1mL硝酸
    分析纯
    氟化氢铵
    优级纯
    氟化氢铵
    Li 7(92.50) 0.017 0.070 0.034 0.031 0.078 0.062
    Be 9(100.00) 0.000 0.002 0.003 0.004 0.008 0.010
    Sc 45(100.00) 0.029 0.299 0.049 0.030 0.152 0.066
    V 51(99.75) 0.229 0.018 0.019 0.231 0.016 0.013
    Cr 52(83.79) 0.230 4.62 0.906 0.144 2.00 0.426
    Co 59(100.00) 0.078 0.316 0.010 0.018 0.133 0.007
    Ni 60(26.10) 0.036 11.73 0.222 0.072 4.87 0.079
    Cu 63(69.17) 0.033 0.152 1.48 0.043 0.038 0.234
    Zn 66(27.90) 0.267 0.601 0.800 0.481 0.494 0.322
    Ga 71(39.90) 0.003 0.002 0.000 0.008 0.017 0.009
    Rb 85(72.17) 0.007 0.028 0.022 0.013 0.019 0.023
    Sr 88(82.58) 0.026 0.010 0.011 0.033 0.098 0.013
    Y 89(100.00) 0.001 0.010 0.007 0.004 0.029 0.015
    Zr 90(51.45) 0.088 0.074 0.069 0.100 0.234 0.072
    Nb 93(100.00) 0.001 0.097 0.051 0.004 0.082 0.052
    Cs 133(100.00) 0.002 0.002 0.003 0.004 0.007 0.008
    Ba 138(71.70) 0.023 0.317 0.193 0.059 0.488 0.390
    La 139(99.91) 0.004 0.015 0.014 0.013 0.022 0.029
    Ce 140(88.48) 0.007 0.026 0.016 0.023 0.048 0.015
    Pr 141(100.00) 0.001 0.003 0.003 0.005 0.006 0.005
    Nd 142(27.12) 0.004 0.012 0.007 0.026 0.020 0.009
    Sm 152(26.70) 0.002 0.003 0.003 0.010 0.005 0.009
    Eu 153(52.20) 0.001 0.001 0.001 0.003 0.001 0.008
    Gd 158(24.84) 0.001 0.003 0.003 0.006 0.007 0.012
    Tb 159(100.00) 0.000 0.000 0.001 0.000 0.001 0.004
    Dy 164(28.20) 0.001 0.002 0.002 0.006 0.009 0.005
    Ho 165(100.00) 0.000 0.000 0.001 0.001 0.001 0.003
    Er 166(33.60) 0.001 0.001 0.001 0.006 0.005 0.004
    Tm 169(100.00) 0.000 0.000 0.000 0.001 0.001 0.002
    Yb 174(31.80) 0.001 0.001 0.001 0.008 0.006 0.003
    Lu 175(97.41) 0.000 0.000 0.000 0.001 0.001 0.002
    Hf 180(35.10) 0.003 0.003 0.004 0.007 0.013 0.010
    Ta 181(99.99) 0.010 0.007 0.010 0.033 0.014 0.028
    Tl 205(70.48) 0.001 0.001 0.002 0.006 0.002 0.005
    Pb 208(52.40) 0.016 0.311 0.151 0.013 0.463 0.374
    Th 232(100.00) 0.001 0.010 0.005 0.004 0.041 0.009
    U 238(99.27) 0.000 0.002 0.002 0.001 0.010 0.003
    注:①数据来源于文献[39]报道的传统硝酸-氢氟酸密闭消解法过程空白和检出限。
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    表 3  氟化氢铵分解方法的精密度

    Table 3.  Method precision test for NH4HF2 decomposition

    待测元素 测定值
    (μg/g)
    标准偏差
    (μg/g)
    RSD
    (%)
    Li 86.5 3.34 3.86
    Be 8.81 0.12 1.39
    Sc 62.5 1.57 3.31
    V 221 4.25 1.92
    Cr 243 7.54 3.10
    Co 6.00 0.19 3.21
    Ni 36.2 0.76 2.10
    Cu 31.4 0.81 2.58
    Zn 26.8 2.53 3.30
    Ga 85.3 2.45 2.88
    Rb 7.94 0.52 8.61
    Sr 693 31.9 4.60
    Y 90.4 2.91 3.61
    Zr 914 24.0 2.35
    Nb 95.2 2.41 2.10
    Cs 0.36 0.03 7.22
    Ba 74.6 2.50 3.35
    La 253 5.39 2.13
    Ce 513 5.84 1.14
    Pr 61.2 1.33 2.18
    Nd 234 4.66 1.99
    Sm 37.4 1.17 3.14
    Eu 7.48 0.58 8.90
    Gd 29.2 1.85 5.56
    Tb 4.21 0.28 6.76
    Dy 23.7 1.60 8.10
    Ho 4.10 0.29 7.05
    Er 12.2 0.92 7.54
    Tm 1.62 0.12 7.43
    Yb 13.3 0.56 4.97
    Lu 1.83 0.12 6.70
    Hf 28.3 0.85 3.51
    Ta 7.96 0.26 3.58
    Tl 0.064 0.004 6.32
    Pb 118 3.25 2.74
    Th 103 3.40 3.31
    U 37.4 1.62 4.34
    下载: 导出CSV
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收稿日期:  2020-03-12
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