Evaluating the reliability of U-Pb laser ablationinductively coupled plasma mass spectrometry (LA-ICP-MS) carbonate geochronology: matrix issues and a potential calcite validation reference material

We document that the reliability of carbonate U-Pb dating by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is improved by matching the aspect ratio of the LA single-hole drilling craters and propagating long-term excess variance and systematic uncertainties. We investigated the impact of different matrices and ablation crater geometries using U-Pb isotope analyses of one primary (WC-1) and two secondary reference materials (RMs). Validation RMs (VRMs) include a previously characterised one (ASH-15D) and a new candidate (JT), characterised by ID-TIMS (intercept age: 13.797 +/- 0.031 Ma) with excellent agreement to pooled LA-ICP-MS measurements (13.75 +/- 0.11 | 0.36 Ma), a U concentration of approx. 1 mu g g(-1) and U-238/Pb-206 ratios from 5 to 460, defining the isochron well. Differences in ablation crater depth to diameter ratios (aspect ratio) introduce an offset due to downhole fractionation and/or matrix effects. This effect can be observed either when the crater size between U-Pb RM and the sample changes or when the ablation rate for the sample is different than for the RM. Observed deviations are up to 20 % of the final intercept age depending on the degree of crater geometry mismatch. The long-term excess uncertainty was calculated to be in the range of 2 % (ASH-15D) to 2.5 % (JT), and we recommend propagating this uncertainty into the uncertainty of the final results. Additionally, a systematic offset to the ID-TIMS age of 2 %-3 % was observed for ASH-15D but not for JT. This offset might be due to different ablation rates of ASH-15D compared to the primary RM or remaining matrix effects, even when the aspect ratios chosen are similar.