Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O2, CO,CO2, N2O and SO2

Gas isotope ratio mass spectrometers usually measure ion current ratios of molecules, not atoms. Often several isotopologues contribute to an ion current at a particular mass‐to‐charge ratio (m/z). Therefore, corrections have to be applied to derive the desired isotope ratios. These corrections are usually formulated in terms of isotope ratios (R), but this does not reflect the practice of measuring the ion current ratios of the sample relative to those of a reference material. Correspondingly, the relative ion current ratio differences (expressed as δ values) are first converted into isotopologue ratios, then into isotope ratios and finally back into elemental δ values. Here, we present a reformulation of this data reduction procedure entirely in terms of δ values and the ‘absolute’ isotope ratios of the reference material. This also shows that not the absolute isotope ratios of the reference material themselves, but only product and ratio combinations of them, are required for the data reduction. These combinations can be and, for carbon and oxygen have been, measured by conventional isotope ratio mass spectrometers. The frequently implied use of absolute isotope ratios measured by specially calibrated instruments is actually unnecessary. Following related work on CO₂, we here derive data reduction equations for the species O₂, CO, N₂O and SO₂. We also suggest experiments to measure the required absolute ratio combinations for N₂O, SO₂ and O₂. As a prelude, we summarise historic and recent measurements of absolute isotope ratios in international isotope reference materials. Copyright © 2008 John Wiley & Sons, Ltd.