Isobaric Spike Method for Absolute Isotopic Ratio Determination by MC-ICP-MS

Absolute isotopic ratios are required for isobaric interference corrections, spike calibrations, and isotopic analysis by external normalization methods. However, high-precision natural isotopic abundance data are lacking for many elements, particularly those with less than four isotopes or having isobaric isotopes with other elements. In this study, we developed a method for absolute isotope ratio analysis, which integrates the concept of the double-spike method with isotopic analysis of element pairs that have isobaric isotopes. Using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS), the isotopic composition of a sample can be derived by measuring a series of mixtures of the sample and a spike element that has an isobaric isotope with the element being analyzed. We applied this method to five pairs of elements (Ca-Ti, V-Ti, Cr-Ti, Ni-Zn, and In-Sn) and obtained the absolute isotopic ratios for Ca, V, Cr, Ni, and In, as well as the relative Ca isotopic composition. By simultaneous measurement of Ti and Ca isotopes, a quantitative relationship between the instrumental mass fractionation factors and element masses was developed. After correcting for the difference in instrumental mass fractionation factors, the obtained absolute ratios agree well with the literature data and have per mil level accuracy. This method has considerable potential in measuring the absolute isotopic ratios of elements that have isobaric isotope with other elements. Such precisely determined absolute isotopic ratios and the relationship between the instrumental mass fractionation factors and elemental masses will improve isobaric interference corrections, particularly when chemical purification is imperfect or during laser ablation analysis.