Prospects of ratio and differential ({\delta}) ratio based measurement-models: a case study for IRMS evaluation

TL;DR

This paper evaluates two measurement models based on ratios and differences for isotope ratio mass spectrometry (IRMS), analyzing their accuracy and suitability for precise isotopic measurements.

Contribution

It clarifies the differences between ratio and differential models and assesses their effectiveness in IRMS evaluation, highlighting the conditions affecting their accuracy.

Findings

Ratio model yA's variation depends on measurement variability.

Differential model yD's accuracy is highly sensitive to measurement ratios.

Using the ratio model improves measurement accuracy and comparability.

Abstract

The suitability of a mathematical-model Y = f({Xi}) in serving a purpose whatsoever (should be preset by the function f specific input-to-output variation-rates, i.e.) can be judged beforehand. We thus evaluate here the two apparently similar models: YA = fA(SRi,WRi) = (SRi/WRi) and: YD = fd(SRi,WRi) = ([SRi,WRi] - 1) = (YA - 1), with SRi and WRi representing certain measurable-variables (e.g. the sample S and the working-lab-reference W specific ith-isotopic-abundance-ratios, respectively, for a case as the isotope ratio mass spectrometry (IRMS)). The idea is to ascertain whether fD should represent a better model than fA, specifically, for the well-known IRMS evaluation. The study clarifies that fA and fD should really represent different model-families. For example, the possible variation, eA, of an absolute estimate as the yA (and/ or the risk of running a machine on the basis of the measurement-model fA) should be dictated by the possible Ri-measurement-variations (u_S and u_W) only: eA = (u_S + u_W); i.e., at worst: eA = 2ui. However, the variation, eD, of the corresponding differential (i.e. YD) estimate yd should largely be decided by SRi and WRi values: ed = 2(|m_i |x u_i) = (|m_i | x eA); with: mi = (SRi/[SRi - WRi]). Thus, any IRMS measurement (i.e. for which |SRi - WRi| is nearly zero is a requirement) should signify that |mi| tends to infinity. Clearly, yD should be less accurate than yA, and/ or even turn out to be highly erroneous (eD tends to infinity). Nevertheless, the evaluation as the absolute yA, and hence as the sample isotopic ratio Sri, is shown to be equivalent to our previously reported finding that the conversion of a D-estimate (here, yD) into Sri should help to improve the achievable output-accuracy and -comparability.