Metal–silicate partitioning studies performed in high-pressure, laser-heated diamond anvil cells (DAC) are commonly used to explore element distribution during planetary-scale core–mantle differentiation. The small run-products contain suitable areas for analysis commonly less than tens of microns in diameter and a few microns thick. Because high spatial resolution is required, quantitative chemical analyses of the quenched phases is usually performed by electron probe microanalysis (EPMA). Here, EPMA is being used at its spatial limits, and sample thickness and secondary fluorescence effects must be accounted for. By using simulations and synthetic samples, we assess the validity of these measurements, and find that in most studies DAC sample wafers are sufficiently thick to be characterized at 15 kVacc. Fluorescence from metal-hosted elements will, however, contaminate silicate measurements, and this becomes problematic if the concentration contrast between the two phases is in excess of 100. Element partitioning experiments are potentially compromised; we recommend simulating fluorescence and applying a data correction, if required, to such DAC studies. Other spurious analyses may originate from sources external to the sample, as exemplified by 0.5 to >1 wt% of Cu arising from continuum fluorescence of the Cu TEM grid the sample is typically mounted on.

The largest differentiation event in Earth and other terrestrial planets was the high-pressure, high-temperature process of metal core segregation from a silicate mantle. The abundant element silicon (Si) can be partially sequestered into the metallic core during metal–silicate differentiation, depending on pressure, temperature and planetary oxidation state. Knowledge of the Si content of a planet's core can constrain the conditions of core formation, but in the absence of direct samples from planetary cores, quantifying core Si content is challenging. One relatively new tool to study core formation in terrestrial planets is based on combining measurements of the Si stable isotopic composition of planetary crust and mantle samples with measurements of the Si stable isotope fractionation between metal and silicate at high-temperature and high-pressure conditions. In this study we present the results of a small set of high-pressure, high-temperature (HPT) experiments and combine these with a review of literature data to investigate how the Si isotope fractionation behaviour between metal and silicate varies as a function specifically of experimental run time and temperature. We show that although there is no debate about the sign of fractionation, absolute values for Si isotope fractionation between metal and silicate are difficult to constrain because the experimental database remains incomplete, and because Si isotopic measurements of metals in particular suffer from the absence of a true inter-laboratory comparison. We conclude that in order to derive accurate quantitative estimates of the Si content of the core of the Earth or other planets a wide range of additional experiments will be required.