Quantifying the impact of recovery during chromatographic purification on the accuracy of lithium isotopic determination by multi-collector inductively coupled plasma mass spectrometry

Rationale: Lithium (Li) isotopes have increasingly been applied as tracers in Earth and planetary sciences and their effectiveness relies upon accurate and precise Li isotopic data. Nowadays, multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) combined with chromatographic purification is the most common strategy for obtaining Li isotopic ratios in natural samples, with a long-term internal precision better than 0.3‰ in most laboratories. However, there is a large discrepancy in the Li isotopic compositions of the same reference materials determined by MC-ICP-MS among international laboratories (e.g. ca 3.5‰ difference for measurements of homogeneous seawater), which has been attributed to insufficient recovery of Li during chromatographic purification. Despite this recognition, the exact impact of Li recovery during purification on Li isotopic determinations by MC-ICP-MS has never been quantified. Methods: We employed a normal distribution function to model Li elution curves and quantified the Li isotopic fractionation resulting from Li recovery during chromatographic purification. Furthermore, we compared the calculated and measured relative recovery (R) with the Li isotopic ratios determined by ICP-MS to validate our theoretical calculation. Results: The theoretical calculations showed that R should be higher than 99.8% in order to avoid observable Li isotopic fractionation during chromatographic purification at IEECAS. This idea is further supported by the better long-term external precisions for data with R ≥ 99.8% compared with previous values of 99.5% ≤ R < 99.8%. Our results indicated that the large differences in the reported Li isotopic ratios for homogeneous seawater among international laboratories are probably attributable to Li isotopic fractionation occurring during ion exchange chromatography. Conclusions: Our theoretical calculation via R is the first quantitative and convenient approach for monitoring Li isotopic fractionation during sample purification, ensuring that R ≥ 99.8% can avoid observable Li isotopic fractionation during purification, which will improve the accuracy of Li isotopic measurements by MC-ICP-MS and the comparability among laboratories.