Study of variations as desired-relative (DELTA), rather than absolute, differences: falsification of the purpose of achieving source-representative and closely comparable lab-results

TL;DR

This paper argues that absolute estimates of source-specific isotopic ratios are more accurate and comparable across labs than relative DELTA estimates, clarifying the limitations of scale conversion and the impact of standards.

Contribution

It provides a fundamental understanding of why absolute isotopic ratios are preferable over relative DELTA estimates for accuracy and comparability, highlighting limitations of scale conversion methods.

Findings

Absolute estimates are more accurate than relative DELTA estimates.

Scale conversion cannot eliminate measurement reference dependence.

Using more standards can decrease estimate accuracy.

Abstract

Recently (arXiv:1101.0973), it has been pointed out by us that the possible variation in any source (S) specific elemental isotopic (viz. 2H/1H) abundance ratio SR can more accurately be assessed by its absolute estimate Sr [viz. as (Sr - DR), with D as a standard-source] than by either corresponding measured-relative (S/W-DELTA) estimate ([Sr/Wr] - 1) or DELTA-scale-converted-relative (S/D-DELTA) estimate ([Sr/DR] - 1). Here, we present the fundamentals behind scale-conversion, thereby enabling to understand why at all Sr should be the source- and/ or variation-characterizing key, i.e. why different lab-specific results should be more closely comparable as absolute estimates (SrLab1, SrLab2) than as desired-relative (S/D-DELTALab1, S/D-DELTALab2) estimates. Further, the study clarifies that: (i) the DELTA-scale-conversion (S/W-DELTA into S/D-DELTA, even with the aid of calibrated auxiliary-reference-standard(s) Ai(s)) cannot make the estimates (as S/D-DELTA, and thus Sr) free of the measurement-reference W; (ii) the employing of (increasing number of) Ai-standards should cause the estimates to be rather (increasingly) inaccurate and, additionally, Ai(s)-specific; and (iii) the S/D-DELTA-estimate may, specifically if S happens to be very close to D in isotopic composition (IC), even misrepresent S; but the corresponding Sr should be very accurate. However, for S and W to be increasingly closer in IC, the S/D-DELTA-estimate and also Sr are shown to be increasingly accurate, irrespective of whether the S/W-DELTA-measurement accuracy could thus be improved or not. Clearly, improvement in measurement-accuracy should ensure additional accuracy in results.