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.
Any physiochemical variable (Ym) is always determined from certain measured variables {Xi}. The uncertainties {ui} of measuring {Xi} are generally a priori ensured as acceptable. However, there is no general method for assessing uncertainty (em) in t
he desired Ym, i.e. irrespective of whatever might be its system-specific-relationship (SSR) with {Xi}, and/ or be the causes of {ui}. We here therefore study the behaviors of different typical SSRs. The study shows that any SSR is characterized by a set of parameters, which govern em. That is, em is shown to represent a net SSR-driven (purely systematic) change in ui(s); and it cannot vary for whether ui(s) be caused by either or both statistical and systematic reasons. We thus present the general relationship of em with ui(s), and discuss how it can be used to predict a priori the requirements for an evaluated Ym to be representative, and hence to set the guidelines for designing experiments and also really appropriate evaluation models. Say: Y_m= f_m ({X_i}_(i=1)^N), then, although: e_m= g_m ({u_i}_(i=1)^N), N is not a key factor in governing em. However, simply for varying fm, the em is demonstrated to be either equaling a ui, or >ui, or even <ui. Further, the limiting error (d_m^(Lim.)) in determining an Ym is also shown to be decided by fm (SSR). Thus, all SSRs are classified into two groups: (I) the SSRs that can never lead d_m^(Lim.) to be zero; and (II) the SSRs that enable d_m^(Lim.) to be zero. In fact, the theoretical-tool (SSR) is by pros and cons no different from any discrete experimental-means of a study, and has resemblance with chemical reactions as well.
In isotope ratio mass spectrometry (IRMS), any sample (S) measurement is performed as a relative-difference ((S/W)di) from a working-lab-reference (W), but the result is evaluated relative to a recommended-standard (D): (S/D)di. It is thus assumed th
at different source specific results ((S1/D)di, (S2/D)di) would represent their sources (S1, S2), and be accurately intercomparable. However, the assumption has never been checked. In this manuscript we carry out this task by considering a system as CO2+-IRMS. We present a model for a priori predicting output-uncertainty. Our study shows that scale-conversion, even with the aid of auxiliary-reference-standard(s) Ai(s), cannot make (S/D)di free from W; and the ((S/W)di,(A1/W)di,(A2/W)di) To (S/D)di conversion-formula normally used in the literature is invalid. Besides, the latter-relation has been worked out, which leads to e.g., fJ([(S/W)dJCO2pmp%],[(A1/W)dJCO2pmp%],[(A2/W)dJCO2pmp%]) = ((S/D)dJCO2pm4.5p%); whereas FJ([(S/W)dJCO2pmp%],[(A1/W)dJCO2pmp%]) = ((S/D)dJCO2pm1.2p%). That is, contrary to the general belief (Nature 1978, 271, 534), the scale-conversion by employing one than two Ai-standards should ensure (S/D)di to be more accurate. However, a more valuable finding is that the transformation of any d-estimate into its absolute value helps improve accuracy, or any reverse-process enhances uncertainty. Thus, equally accurate though the absolute-estimates of isotopic-CO2 and constituent-elemental-isotopic abundance-ratios could be, in contradistinction any differential-estimate is shown to be less accurate. Further, for S and D to be similar, any absolute estimate is shown to turn out nearly absolute accurate but any (S/D)d value as really absurd. That is, estimated source specific absolute values, rather than corresponding differential results, should really represent their sources, and/ or be closely intercomparable.
Evaluation of a variable Yd from certain measured variable(s) Xi(s), by making use of their system-specific-relationship (SSR), is generally referred as the indirect measurement. Naturally the SSR may stand for a simple data-translation process in a
given case, but a set of equations, or even a cascade of different such processes, in some other case. Further, though the measurements are a priori ensured to be accurate, there is no definite method for examining whether the result obtained at the end of an SSR, specifically a cascade of SSRs, is really representative as the measured Xi-values. Of Course, it was recently shown that the uncertainty (ed) in the estimate (yd) of a specified Yd is given by a specified linear combination of corresponding measurement-uncertainties (uis). Here, further insight into this principle is provided by its application to the cases represented by cascade-SSRs. It is exemplified how the different stage-wise uncertainties (Ied, IIed, ... ed), that is to say the requirements for the evaluation to be successful, could even a priori be predicted. The theoretical tools (SSRs) have resemblance with the real world measuring devices (MDs), and hence are referred as also the data transformation scales (DTSs). However, non-uniform behavior appears to be the feature of the DTSs rather than of the MDs.
