Uncertainty of Blank Correction in Isotope Ratio Measurement

Abstract

Blank correction for isotope ratio measurement on small amounts of substances is often limited by presence of a blank, with an apparent isotopic composition different from that of the sample. For isotope ratios, blank correction is commonly performed either by the regression method, which works without the need for estimation of the blank, or by the subtraction method. With the subtraction method, estimation of the amount and isotope delta of the blank is required, and these estimates could be obtained either by direct, semi-indirect, or indirect measurement. Previously given expressions for the standard uncertainties of indirectly measured blank amounts and blank isotope deltas did not account for covariance between input quantities. In the present work, a previously published data set was re-evaluated, with covariance terms properly included in the calculation of uncertainties. It was shown that covariance effects may yield a significant reduction in uncertainty estimates, both for blank quantities and for blank corrected results. For series measurements on a standard material, it was also shown that the distribution of individual corrected isotope delta values around the average value was approximately normal, with its standard deviation equal to the estimated standard uncertainty of the corrected values. In most cases, it was observed that the regression and subtraction methods yield approximately the same blank corrected average values and uncertainties, regardless of method selected for estimation of blank quantities.

A closer look into the nitrogen blank in elemental analyser/isotope ratio mass spectrometry measurements

“…From the intersection of the resulting regression lines (inserts in Figure 1, Figure 2), the N blank amount and isotopic composition can be interpolated. 6 Following the suggestion of Brand and Coplen, 8 the isotopic compositions at natural abundance levels are expressed in mUr, where mUr is equivalent to the traditional ‰.…”

“…The nitrogen blank from “open” tin capsules was determined by plotting the sample isotopic composition vs 1/sample amount in a Keeling‐plot (Figure ). From the intersection of the resulting regression lines (inserts in Figure , Figure ), the N blank amount and isotopic composition can be interpolated …”

“…[1][2][3][4][5] All these methods suffer from increasing influence from the analytical blanks with decreasing sample size, and correction of blank effects may be necessary. 6 While correction for the C blank is relatively straightforward as its origin is known 2 and the amount and isotopic composition can be measured, 2,5 the correction of N blanks is not as straightforward. This is probably because a number of sources may contribute to the total N blank of an EA/IRMS measurement.…”

Successive and automated stable isotope analysis of CO2, CH4 and N2O paving the way for unmanned aerial vehicle‐based sampling

“…While there were no peaks at the retention time of N 2 O in blank measurements, there was a small peak interfering with the CH 4 peak. These blank peaks were similar in AreaAll and δ 13 C values in measurements of multiple blank vials within each sequence which enabled a straightforward subtraction from calibration gas standards and sample values 37 …”

Evaluation strategies and uncertainty calculation of isotope amount ratios measured by MC ICP-MS on the example of Sr

“…Most authors apply a simplified uncertainty calculation based on the assumption that estimates of input quantities are not correlated. The uncertainty of isotope amount ratios can, however, be significantly affected by disregarded correlations [ 73 , 74 ]. In the GUM workbench software the consideration of correlations can easily be included by entering correlation coefficients into the correlation matrix.…”