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    地质样品卤族元素分析进展

    何焘 汪在聪 胡兆初

    何焘, 汪在聪, 胡兆初, 2021. 地质样品卤族元素分析进展. 地球科学, 46(12): 4452-4469. doi: 10.3799/dqkx.2021.117
    引用本文: 何焘, 汪在聪, 胡兆初, 2021. 地质样品卤族元素分析进展. 地球科学, 46(12): 4452-4469. doi: 10.3799/dqkx.2021.117
    He Tao, Wang Zaicong, Hu Zhaochu, 2021. Advances in Analysis for Halogens in Geological Materials. Earth Science, 46(12): 4452-4469. doi: 10.3799/dqkx.2021.117
    Citation: He Tao, Wang Zaicong, Hu Zhaochu, 2021. Advances in Analysis for Halogens in Geological Materials. Earth Science, 46(12): 4452-4469. doi: 10.3799/dqkx.2021.117

    地质样品卤族元素分析进展

    doi: 10.3799/dqkx.2021.117
    基金项目: 

    国家自然科学基金面上项目 41873029

    详细信息
      作者简介:

      何焘(1992-), 男, 博士后, 主要从事分析地球化学研究.ORCID: 0000-0002-1074-2089.E-mail: taohe1992@sina.com

    • 中图分类号: P599

    Advances in Analysis for Halogens in Geological Materials

    • 摘要: 地质样品中卤素是反演与流体和挥发分相关的地质过程的重要示踪元素.由于卤素含量低和强挥发性,准确测定地质样品中卤素一直是分析地球化学的难点.近年来,针对地质样品卤素的样品前处理技术的开发开展了大量工作.高温热解法、碱熔(溶)法、酸性消解法和碱性提取法能够满足土壤、沉积物和岩石中高含量卤素的分析要求.针对低含量卤素,仅有中子活化法和稀有气体质谱法能够准确定量.随着分析地球化学的发展,地质样品卤素分析技术逐渐向更高效的消解方法、更简便的操作以及更高灵敏度和高精度的分析方向改进.总结了近年来国内外在地质样品卤素分析方面所取得的成果,对比了各类方法的优缺点,展望了地质样品卤素分析方法的发展前景.

       

    • 图  1  地球上不同卤素储库的Br/Cl和I/Cl比值与不同矿床类型流体的Br/Cl和I/Cl比值(改自Lecumberri-Sanchez and Bodnar, 2018)

      Fig.  1.  Characteristic Br/Cl and I/Cl ratios of the different halogen reservoirs on the Earth and fluids in different ore deposit types(revised from Lecimberri-Sanchez and Bodnar, 2018)

      图  2  国内土壤(GSS系列)和沉积物(GSD系列)标准物质和国际岩石标准物质(玄武岩BHVO-2、安山岩AGV-2、花岗岩GS-N和橄榄岩JP-1)中Br (a)和I (b)的测定值

      Fig.  2.  The measured values of Br (a) and I (b) in reference standard materials including soils (GSS series), sediments (GSD series) and rocks (basalt BHVO-2, andesite AGV-2, granite GS-N and peridotite JP-1)

      图  3  高温热解法装置(改自Chai and Muramatsu, 2007)

      Fig.  3.  The schematic diagram of pyrohydrolysis (revised from Chai and Muramatsu, 2007)

      图  4  氟化氢铵消解卤素分析方法机理图(改自He et al., 2019)

      Fig.  4.  The decomposition mechanism of NH4HF2 digestion for halogen analysis (revised from He et al., 2019)

      图  5  79Br中子活化过程示意(改自Ruzié-Hamilton et al., 2016)

      Fig.  5.  The schematic of neutron irradiation for 79Br(revised from Ruzié-Hamilton et al., 2016)

      图  6  在电离温度Tion=7 500 K时,理论计算的各元素的电离程度

      Fig.  6.  Calculated values for degree of ionization of various elements at Tion=7 500 K

      表  1  地球各个储库的卤素丰度

      Table  1.   Abundances of halogens on Earth

      储库类型 储库总质量(1021 kg) F(μg/g) Cl(μg/g) Br(μg/g) I(μg/g)
      海水 1.4±0.7 1.30±0.07 19 300±970 66±3.3 0.058±0.006
      蒸发盐 0.030±0.005 10±10 550 000±50 000 150±100 1±1
      海洋沉积物 0.5±0.1 1 000±300 4 000±3 000 40±20 30±15
      沉积岩 1.5±0.3 550±100 700±400 4±3 1.5±1.0
      地壳卤水 0.06±0.03 20±15 100 000±50 000 600±400 15±10
      地壳 26±3 550±100 300±100 0.60±0.25 0.018±0.009
      地幔 2 800±800 12±2 5±2 0.013±0.006 0.000 3±0.000 01
      原始地幔 4 040 17±6 26±8 76±25 0.007±0.004
        注:数据引自Kendrick et al.(2017).
      下载: 导出CSV

      表  2  卤素的质谱干扰所需分辨率

      Table  2.   The resolution to resolve the spectral interferences on halogens

      被测元素 干扰离子 所需分辨率(M/ΔM)
      19F+ 38Ar2+ 1 116
      18O1H+ 1 160
      35Cl+ 19F16O+ 1 430
      18O18O1H+ 1 059
      37Cl+ 36Ar1H+ 4 680
      79Br+ 63Cu16O+ 12 790
      41K38Ar+ 12 688
      39K40Ar+ 10 184
      40Ar38Ar1H+ 5 405
      81Br+ 65Cu16O+ 12 624
      45Sc36Ar+ 11 286
      41K40Ar+ 10 217
      63Cu18O+ 6 489
      40Ar40Ar1H+ 4 965
      127I+ 87Sr40Ar+ 3 822
      87Rb40Ar+ 3 854
      111Cd16O+ 23 545
      下载: 导出CSV
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