碳酸盐岩样品中团块同位素CO2精确分析的新评价策略

M. Mandić, Mario Tuthorn, Nils Stoebener, J. Radke, J. Schwieters
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引用次数: 0

摘要

长积分双进样(LIDI)是一种成熟的技术,通过对整个样品和参比物进行顺序测量,而不是像传统的双进样方法那样在较短的时间内在样品和参比物之间交替进行,从而提高了对碳酸盐样品分析的准确性和精密度。到目前为止,有两个关键的挑战限制了进一步改进Δ47测定:在长时间测量样品和参比气体期间,IRMS必须处于稳定的温度环境中,样品和参比毛细管的压痕必须精确匹配,否则产生的数据将不准确,精度降低。在这里,我们介绍了对样品气体测量和数据评估所做的改进,我们将其定义为LIDI 2。通过应用LIDI 2方法,可以按照四步方法进行样本套接,从而完全纠正温度漂移(即从数据中消除),将标准偏差降低2倍。对于获得团块同位素数据来说,这是一个巨大的进步,因为要达到非常稳定的温度(0.1℃/h)对大多数实验室来说是一个挑战。除了消除由实验室空气温度不稳定引起的数据变化外,LIDI 2还改善了由于毛细血管不完美卷曲而导致的样品和参比气体信号的重叠。卷曲过程是费力的,很少提供完美的结果。此外,参考测量前的压力调整必须确保样品强度和参考强度之间没有明显的偏移。LIDI 2提供了完美的样品与参比强度匹配,这大大提高了每种样品气体分析的精度。单样品测量的标准误差提高了2倍。LIDI 2方法在小型碳酸盐样品的测量上提供了更高的准确度和精度,结合惰性毛细管涂层和自动污染物捕获的最新进展,有助于提高团块同位素数据质量。
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LIDI 2 – New Evaluation Strategy for Accurate and Precise Clumped Isotope CO2 Analysis on Carbonate Samples

Long Integration Dual Inlet (LIDI) is an established technology which enabled improved accuracy and precision of Δ47 analysis from carbonate samples by utilizing sequential measurement of the full sample and reference, rather than alternating between sample and reference on shorter time periods, as it is done in the classical Dual Inlet method. As of today, there are two key challenges that were limiting further improvements to Δ47 determination: the IRMS must be in a stable temperature environment during long measurement of sample and reference gas, and the crimping of the sample and reference capillaries must be precisely matched, otherwise the produced data will be inaccurate and have reduced precision.

Here we present the improvements made on the sample gas measurement and data evaluation, which we define as LIDI 2.

By applying the LIDI 2 method, sample bracketing is possible following a four-step approach, resulting in fully corrected temperature drift (i.e. eliminated from the data), decreasing the standard deviation by factor of 2. This is a substantial improvement for acquiring clumped isotope data as reaching a very stable temperature of ±0.1°C/h is a challenge for most laboratories.

Alongside eliminating variation in the Δ47 data caused by unstable laboratory air temperature, LIDI 2 also improves the overlap of sample and reference gas signals due to non-perfect crimping of the capillaries. The crimping procedure is laborious and rarely delivers perfect results. Additionally, the pressure adjustment before reference measurement must ensure there is no significant offset between sample and reference intensities. LIDI 2 delivers perfect sample versus reference intensity matching, which results in significantly higher precision on each sample gas analyzed. Standard error of a single sample measurement is improved by up to factor of 2.

The LIDI 2 method delivers improved accuracy and precision on Δ47 measurement from small Carbonate samples, which in combination with the latest advancements in inert capillaries coating and automated contaminant trapping contributes to enhanced clumped isotopes data quality.

 

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