Compensation of isotope ratio mismatch in double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP/MS)

Abstract

Abstract Exact-matching double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP/MS) is widely used to characterize reference materials (RMs) in elemental analysis. In this technique, achieving exactly matching isotope ratios for the sample and calibration blends is regarded as an important prerequisite for obtaining accurate measurement results. However, meeting this condition requires multiple time-consuming iterative measurements. In the current study, an alternative approach that can avoid lengthy iterative procedures while maintaining the accuracy of the ID-ICP/MS results was successfully investigated. We examined the effects of an extensively wide range of inexact-matching isotope ratios (approximately 75%–130%) in double ID-ICP/MS for elements with a wide mass range. Our experimental study, using gravimetrically prepared samples of Ca, Cd, Cu, Fe, Hg, Mg, Ni, Pb, and Zn, demonstrated that, despite deliberately introducing mismatching of isotope ratios, the accuracy of the ID-ICP/MS results remained consistent with relative measurement bias of typically less than 0.5%. The absence of a systematic bias due to deviations in the sample blend isotope ratios from the target ratios of the calibration blends revealed that the variability due to an isotope ratio mismatch was sufficiently compensated for. Furthermore, the expanded measurement uncertainties were sufficiently small with negligible variations observed across the different matching ratios. Typically, they were less than 1%, except for Fe, Hg, Pb, and Zn which were less than 2%. This assertion is also supported by theoretically calculated error magnification factors. Consequently, it is feasible to directly utilize the marginally estimated mass fraction of the analyte of interest without extensive iterative measurements. The findings of this study provide robust data for ID-ICP/MS, allowing to circumvent lengthy iterative procedures while maintaining the accuracy and precision of the measurement results, particularly in the characterization of RMs for elemental analysis.