West Australian Biogeochemistry Centre and John de Laeter Centre of Mass Spectrometry, School of Plant Biology, The University of Western Australia, 35 Stirling Highway (MO90), Crawley, WA 6009, Australia.
Rapid Commun Mass Spectrom. 2011 Jun 15;25(11):1625-30. doi: 10.1002/rcm.5032.
The propagation of uncertainties associated with the stable oxygen isotope reference materials through a multi-point normalisation procedure was evaluated in this study using Monte Carlo (MC) simulation. We quantified the normalisation error for a particular selection of reference materials and their number of replicates, when the choice of standards is restricted to either nitrates, sulphates or organic reference materials alone, and in comparison with when this restriction was relaxed. A lower uncertainty in stable oxygen isotope analyses of solid materials performed using High-Temperature Pyrolysis (HTP) can be readily achieved through an optimal selection of reference materials. Among the currently available certified reference materials the best performing pairs minimising the normalisation errors are USGS35 and USGS34 for nitrates; IAEA-SO-6 and IAEA-SO-5 for sulphates; and IAEA-601 and IAEA-602 for organic materials. The normalisation error can be reduced further--by approximately half--if each of these two analysed reference materials is replicated four times. The overall optimal selection among all nine considered reference materials is the IAEA-602 and IAEA-SO-6 pair. If each of these two reference materials is replicated four times the maximum predicted normalisation error will equal 0.22‰, the minimum normalisation error 0.12‰, and the mean normalisation error 0.15‰ over the natural range of δ(18)O variability. We argue that the proposed approach provides useful insights into reference material selection and in assessing the propagation of analytical error through normalisation procedures in stable oxygen isotope studies.
本研究采用蒙特卡罗(MC)模拟评估了通过多点归一化程序传播与稳定氧同位素参考物质相关的不确定度。我们量化了特定参考物质及其重复次数的归一化误差,当标准选择仅限于硝酸盐、硫酸盐或有机参考物质时,以及当放宽此限制时。通过优化参考物质的选择,可以轻松实现使用高温热解法(HTP)对固体材料进行稳定氧同位素分析的更低不确定性。在当前可用的认证参考物质中,表现最佳的最小化归一化误差的最佳对是硝酸盐中的 USGS35 和 USGS34;硫酸盐中的 IAEA-SO-6 和 IAEA-SO-5;以及有机材料中的 IAEA-601 和 IAEA-602。如果将这两种分析的参考物质分别重复四次,归一化误差可以进一步降低约一半。在考虑的所有九个参考物质中,整体最佳选择是 IAEA-602 和 IAEA-SO-6 对。如果这两种参考物质的每个重复四次,最大预测归一化误差将等于 0.22‰,最小归一化误差为 0.12‰,平均值归一化误差为 0.15‰,涵盖了 δ(18)O 变异性的自然范围。我们认为,所提出的方法为参考物质选择提供了有用的见解,并评估了稳定氧同位素研究中通过归一化程序传播分析误差的情况。