On the pros and cons of the IRMS technique of data processing: uncertainty in results, a case study for determining carbon and oxygen isotopic abundance ratios as CO_2^+

Physics – Data Analysis – Statistics and Probability

Scientific paper

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Revised version with a clarifying APPENDIX on notations: 32 pages (including 6 Tables)

Scientific paper

In isotope ratio mass spectrometry (IRMS), the sample data are acquired and processed by a recommended design. The idea behind the design is that any result of analysis should be accurate and comparable with other relevant results. However, whether the purpose is really served was in no way crosschecked. We here however show that, by studying the behavior of relationship(s) representing an IRMS analysis, the state of art viz. whether redesigning of evaluation scheme is required can even a priori be ascertained. We discuss our process and findings for the system as CO_2^+ IRMS. It is thus shown that the (scale) conversion of measured differential isotopic-CO_2^+ abundance ratios into the absolute ratios by using only one auxiliary reference standard helps improve data-accuracy even, depending on the working reference used, tens of folds. However, the employment of an additional auxiliary standard in the process causes no further betterment of data-accuracy. In fact, the corresponding formula is not valid. Another formula, enabling the use of two and even any larger number of auxiliary reference standards, is here logically worked out. However, the same is observed to represent an error-enhancing process. The process of evaluating constituent elemental isotopic abundance ratios is a little involved as solving a set of equations. Yet, it is here exemplified that, and explained why, the evaluated 13C/12C, 17O/16O and 18O/16O ratios are as representative as their inputs (scale converted isotopic CO2 abundance-ratios). However, transformation of an estimate into the relative difference from a reference value is shown to be accomplished by uncertainty-enhancement. That is any estimate should be better accurate, and hence comparable, as its absolute value than as the so-called "DELTA".

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