元素分析-同位素质谱测定δ15N和δ34S的信号强度响应特征

Effect of Sample Signal Intensity on δ15N and δ34S Measurement by EA-IRMS System

  • 摘要: 自然界中不同类型样品C、N和S元素含量以及C/N和C/S的差异极大,导致元素分析-同位素比值质谱仪(EA-IRMS)联机系统的进样量和检测信号强度的变化范围极大。进样量和信号强度对EA-IRMS测定δ15N和δ34S的影响将导致样品测量结果具有较大的不确定性。为应对样品中目标元素含量低或样品稀缺等限制,本研究重点关注EA-IRMS测定δ15N和δ34S的信号强度依赖性特征。结果表明,EA-IRMS在小元素进样量或弱信号强度条件下测定δ15N和δ34S需要进行空白校正。在1.71~561.93 μg N和3.74~100.62 μg S的进样条件下,同位素标准物质δ15N和δ34S的测定误差变化范围分别为0.18‰~0.54‰和0.21‰~0.88‰,测定精度变化范围分别为0.24‰~0.57‰和0.27‰~0.54‰。该联机系统对高C/N和C/S(>200)木材标准物质测定时,其δ15N平均误差为0.34‰,其δ34S的测定精度为0.58‰。此外,对两种木材样品δ15N的连续(6~20 d)测定证明该联机系统的测定结果具有较好的时间稳定性。该研究可为EA-IRMS技术的应用与发展提供数据参考。

     

    Abstract: Carbon-nitrogen ratio (C/N) and carbon-sulphur ratio (C/S) of unknown samples can vary greatly in the natural environment. There are also distinct differences in the ionization efficiencies of N and S elements. These factors will introduce the fluctuation of signal intensity to the element analysis-isotope ratio mass spectrometry (EA-IRMS), which can has a further impact on the measurements of sample δ15N and δ34S. However, the analysis of unknown sample δ15N and δ34S is always restricted by the low content or the scarcity of the target elements. In this study, we focused on the effect of sample amount and signal intensity on the δ15N and δ34S measurement by EA-IRMS. Our results indicated that the EA-IRMS measurement of δ15N and δ34S was significantly affected by the “blank effect” when the sample amount and signal intensity were limited during the mass spectrometry analysis. Under the injection conditions of 1.71-561.93 μg N and 3.74-100.62 μg S, the variation ranges of the measurement errors of the isotopic reference materials δ15N and δ34S were 0.18‰-0.54‰ and 0.21‰-0.88‰, respectively. Meanwhile, the variation ranges of the measurement errors of measurement precision were 0.24‰-0.57‰ and 0.27‰-0.54‰, respectively. With the high C/N and C/S wood samples, the measurement errors of EA-IRMS were 0.34% for δ15N. Because the true value of the above wood sample δ34S was unknown, the measurement precision of EA-IRMS on the wood samples was 0.58‰. Based on the analysis of two wood sample δ15N, the EA-IRMS had a good time stability during the continuous (6-20 days) measurement process. We hoped these findings could provide implications for the application of EA-IRMS in biogeochemistry and life science areas.

     

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