超微量(80nanomole)硫化物硫酸盐硫同位素的EA-IRMS测试
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中国地质科学院矿产资源研究所

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国家自然科学基金项目(面上项目,重点项目,重大项目)


Measurements of Sulfur Isotope Composition on Ultrasmall (80 nanomole) Sulfide and Sulfate Samples by EA-IRMS
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Chinese Acadamy of Geological Sciences

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    摘要:

    常规EA-IRMS进行硫同位素测试时需硫量大于2 μmol,这限制了该技术在测试含硫量低的样品时的使用。如此大的需硫量是因为He载气携带样品气体在经过元素分析仪(EA)时的流速为~100 mL/min,而气体同位素质谱仪仅允许气体以低流速进入,所以99.7%的混合气体会通过连续流接口排出,以保证混合气体以~0.3 mL/min的流速通过连续流接口。因此,大部分的样品气体会被浪费,样品的利用率仅有0.3%。在本研究中,我们将自主研发的冷冻富集、分离与纯化系统与EA-IRMS联用测试了六种标准物质的硫同位素,并检测该系统的表现。实验结果表明,使用本研究中改进的方法进行硫化物和硫酸盐标准物质的硫同位素测试,得到的硫同位素结果与常规方法一致,即需硫量仅80 nmol即可得到硫同位素测试结果精度 ±0.24‰–±0.76‰ (1σ),与使用吸附柱进行硫同位素测试的方法获得的精度相似。所以,改进后的EA-IRMS可以实现超微量硫化物、硫酸盐的硫同位素测试。此外,本方法也可应用至需样量低至100 nmol的碳、氮和氧同位素分析测试工作中。

    Abstract:

    The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such large sample size limits its application to low-S materials., and is mainly due to the ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of continuous-flow interface. A modified EA-IRMS system with a gas chromatographic (GC) column and a custom-built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA-IRMS. Precisions ranging from ±0.24‰–±0.76‰ (1σ) can be obtained with samples equivalent to ~80 nmol sulfur, which were similar to an alternative method using absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, and can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.

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  • 收稿日期:2021-02-19
  • 最后修改日期:2021-05-26
  • 录用日期:2021-05-29
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