Synthesising homogeneous carbonate reference materials for in situ U–Pb calcite geochronology

Recent years have seen a rise in applications of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to elemental and isotopic analysis of a wide range of geological materials, with a true explosion of in situ geochronology. Standardising such analyses relies on a homogeneous matrix-matched primary reference material (RM) whose ablation, transport and ionisation characteristics will result in fractionating elements and isotopes in the same way as in the unknown of interest. One of the current frontiers of LA-ICP-MS geochronology – U–Pb dating of carbonates – suffers from a lack of such a material. Because the currently used primary RMs (e.g. WC-1 [1]) are heterogeneous in both age and U/Pb ratio, isotopic ratios are corrected on an isochron (whole-sample) basis rather than for each individual analytical spot, which imposes excess uncertainty on all U–Pb ages obtained this way. The U–Pb carbonate geochronology community is thus in urgent need of homogeneous reference materials for wide distribution. Ideally, such a RM should match the ablation behaviour of the unknown carbonate and consequently all matrix effects, including the amount and depth progression of inter-element laser induced elemental fractionation (LIEF), can be corrected directly, as is standard in e.g. zircon U–Pb geochronology. We present a method for preparing synthetic RMs that uses a natural rock starting material which is milled to nano-powder, homogenised, and recrystallised using high-pressure, high-temperature apparatuses. In this way, natural sample heterogeneity is removed through milling, while textural coarsening is aimed at generating ablation behaviour similar to that of routine unknown samples. Initial tests of synthetic calcite materials demonstrate the ability to achieve homogeneity at the spatial scale of a typical LA-ICP-MS laser spot size (80–110 µm typical for calcite U–Pb), while the ablation rate and LIEF are comparable to those of a range of commonly used calcite RMs. This suggests that experimental manufacturing of recrystallised carbonate is a promising avenue to obtain primary RMs that will allow spot-by-spot correction of LIEF in U–Pb analyses, thereby significantly reducing the reliance on heterogenous natural calcite RMs and improving the precision and accuracy of this analytical method. Finally, this approach may serve as a blueprint for larger-scale production of primary RMs for a variety of matrices and isotopic systems for which there are no natural RMs characterised by the necessary homogeneity or availability. [1] Roberts, N.M.W., et al., Geochemistry Geophysics Geosystems, 2017, 18(7): 2807-2814.