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水中系列氢氧同位素标准物质的研制

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张琳, 刘福亮, 贾艳琨, 刘君. 水中系列氢氧同位素标准物质的研制[J]. 岩矿测试, 2013, 32(5): 7/80-784.
引用本文: 张琳, 刘福亮, 贾艳琨, 刘君. 水中系列氢氧同位素标准物质的研制[J]. 岩矿测试, 2013, 32(5): 7/80-784.
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Lin ZHANG, Fu-liang LIU, Yan-kun JIA, Jun LIU. Preparation and Certification of Reference Materials for Hydrogen and Oxygen Isotopes in Water[J]. Rock and Mineral Analysis, 2013, 32(5): 7/80-784.
Citation: Lin ZHANG, Fu-liang LIU, Yan-kun JIA, Jun LIU. Preparation and Certification of Reference Materials for Hydrogen and Oxygen Isotopes in Water[J]. Rock and Mineral Analysis, 2013, 32(5): 7/80-784.
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水中系列氢氧同位素标准物质的研制

  • 中国地质科学院水文地质环境地质研究所，河北 正定 050803

  • 基金项目:
    中国地质大调查项目(1212011120290)
详细信息
    作者简介: 张琳，副研究员，从事地下水同位素研究。E-mail: zhl5369@163.com

  • 中图分类号: TQ421.31;O628.11;O628.41

Preparation and Certification of Reference Materials for Hydrogen and Oxygen Isotopes in Water

  • Institute of Hydrogeology and Environmental Geology,Chinese Academy of Geological Sciences,Zhengding 050803,China

    摘要
  • 我国氢氧同位素国家一级标准物质经过二十余年的使用，现已不能满足需求，急需研制代表当今分析技术水平的新的氢氧同位素国家标准物质。本文研制了系列(4个)水中氢氧同位素标准物质，其中三个采自天然水样，一个为人工配制的贫氘水，三种天然水样基本涵盖了我国境内天然水的氢氧同位素组成范围。每种标准物质随机抽取30瓶的均匀性子样，每份子样做双份分析，进行均匀性检验，四种标准物质的均匀性检验得到的F值都小于相应的自由度的临界值，显示四种标准物质的均匀性良好。标准物质的δ18O和δD值经过2年的稳定性检验，特征量值变化在不确定度范围，由此判定δD、δ18O值稳定性良好。采用国际间实验室采用不同原理的方法协同定值，11家国内外实验室分别采用Cr还原法、激光法、H2-H2O平衡法、高温热转换元素分析法进行水中氢同位素定值，采用CO2-H2O平衡法进行氧同位素定值；定值不确定度显著降低，δ18O的扩展不确定度小于0.08‰，δD的扩展不确定度小于0.9‰。该标准物质已被国家质检总局批准确为国家一级标准物质,批准号为GBW 04458～GBW 04461。
    Certified reference materials of water for stable hydrogen and oxygen isotopes were developed and have been used for more than 30 years. However, they no longer meet the requirements for newly developed technologies. New reference materials of water have been developed, including three natural water samples and one artificially deuterium depleted water sample and are discussed in this paper. The three natural water samples mostly cover the range of δ18O and δD values for the majority of natural water in China. 30 ampoules were selected randomly from the 5000 ampoules for homogeneity test and each sample was measured twice. According to the homogeneity test results, no statistically significant heterogeneity was found based on the F test. The verified results by variance analysis for four material samples showed very good homogeneity for the series. Nearly two years of stability analysis of δ18O and δD values confirm that they have no statistically significant instability. The certified values of the reference materials were determined by an inter-laboratory comparison of 11 participating laboratories, using different measurement methods and instruments. Uncertainty assessment was performed. The δD value of the reference materials was determined by the chromium-reduction method, H2-H2O equilibration using platinum as a catalyst, laser-based stable isotope measurement, and high-temperature conversion/elemental analysis-isotope ratio mass spectrometry (elemental analyzer systems; IRMS). The δ18O value of the reference materials was determined primarily by the classic CO2-H2O equilibration method. The expanded uncertainties at the 95% confidence level of δ18O were less than 0.08‰ and δD was less than 0.9‰. The reference materials were approved as certified reference materials by AQSIQ, China (State General Administration of the People’s Republic of China for Quality Supervision and Inspection and Quarantine) in 2012. The serial numbers are GBW 04458-GBW 04461.
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  • 表 1  δ18O均匀性检验方差分析结果

    Table 1.  Variance analysis for δ18O homogeneity inspection of reference sample

    δ18OQ2ν2s22Q1ν1s12FFα(ν1,ν2)
    OH10.1539300.00510.1682290.00581.131.85
    OH20.15410.00510.18280.00631.23
    OH30.46710.01560.46630.00161.03
    OH40.94870.03160.92480.03191.01
    下载: 导出CSV

    表 2  δD均匀性检验方差分析结果

    Table 2.  Variance analysis for δD homogeneity inspection of reference sample

    δDQ2ν2s22Q1ν1s12FFα(ν1,ν2)
    OH114.1236300.470814.5145290.50051.061.85
    OH212.95800.4319 10.58600.3650 0.85
    OH315.88490.5295 18.31260.6315 1.19
    OH434.06701.1356 34.04441.1739 1.03
    下载: 导出CSV

    表 3  δ18O标准溶液稳定性检验结果

    Table 3.  The stability test of δ18O values for the four reference materials

    δ18O1361224均值标准偏差
    s
    OH1-0.19-0.14-0.16-0.24-0.15-0.180.040
    OH2-8.64-8.70-8.63-8.72-8.62-9.660.045
    OH3-19.03-19.13-19.13-19.11-19.14-19.110.045
    OH4-55.80-55.73-55.81-55.79-55.82-55.790.035
    下载: 导出CSV

    表 4  δD标准溶液稳定性检验结果

    Table 4.  The stability test of δD values for the four reference materials

    δD141224均值标准偏差
    s
    OH1-2.34-2.11-2.17-1.61-2.060.32
    OH2-63.27-63.28-63.39-63.26-63.300.06
    OH3-143.02-143.55-143.15-143.95-143.420.42
    OH4-433.87-433.08-433.64-433.63-433.560.34
    下载: 导出CSV

    表 5  各实验室的分析数据

    Table 5.  Multiple measurement data of δD for the four reference materials

    实验室编号δDVSMOW/‰
    OH1OH2OH3OH4
    1-1.55-63.20-143.93-432.19
    2-1.52-62.72-143.43-433.68
    3-1.35-62.92-144.38-434.26
    4-2.17-63.39-143.15-433.64
    5-1.61-63.26-143.95-433.63
    6-2.30-63.69-144.20-433.90
    7-2.08-63.85-144.37-432.03
    8-3.68*-63.67-143.32-432.92
    9-1.56-63.19-144.10-434.21
    10-1.79-64.11-145.03-433.36
    11-1.50-63.25-143.71-433.27
    12-1.71-63.88-144.54-432.59
    注：“*”表示剔除数据。
    下载: 导出CSV

    表 6  各实验室δ18O的分析数据

    Table 6.  Multiple measurement data of δ18O for the four reference materials

    实验室编号δ18OVSMOW/‰
    OH1OH2OH3OH4
    1-0.14-8.55-19.09-55.72
    2-0.16-8.63-19.13-55.81
    3-0.16-8.62-19.16-55.91
    4-0.12-8.66-19.15-55.82
    5-0.16-8.67-19.19-55.67
    6-0.20-8.56-19.01-55.54
    7-0.10-8.61-19.17-55.80
    8-0.19-8.60-19.12-55.71
    9-0.16-8.63-19.20-55.70
    10-0.14-8.55-19.09-55.72
    下载: 导出CSV

    表 7  标准物质定值元素δ18O、δD的认定值及扩展不确定度

    Table 7.  δ18O and δD reference values for materials OH1 to OH4 and their associated expanded uncertainties (k=2)

    项目OH1OH2OH3OH4
    标准值及扩展不确定度
    δ18OVSMOW/‰    		-0.15±0.07-8.61±0.08-19.13±0.07-55.73±0.08
    标准值及扩展不确定度
    δDVSMOW/‰    		-1.7±0.4-63.4±0.6-144.0±0.8-433.3±0.9
    下载: 导出CSV
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收稿日期:  2012-12-13
录用日期:  2013-03-06

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