In situ investigation of the atomic structure of carbonate-silicate liquids at high pressure-temperature and spectroscopic characterization of the recovered quenched glasses

Abstract

Carbonate-silicate melts that originate in Earth's interior are described as transitional melts which possess compositions intermediate between carbonatitic and basaltic end members. The covariation of key oxides between carbonatite and basalt (e.g., 10–35 wt% SiO2 and 40–10 wt% CO2, respectively) is expected to have a strong effect on liquid properties. However, due to their paucity both in the record of terrestrial rocks and as quenched glasses, their molecular structure has remained poorly explored to date. We investigated the atomic structure of a synthetic carbonate-silicate liquid with chemical composition within the CaO-MgO-Al2O3-SiO2-FeO-Na2O-ClO−-CO2 oxide system having 18.28 wt% SiO2 and 22.54 wt% CO2 using multi-angle energy dispersive X-ray diffraction at pressures (P) and temperatures (T) of 1.4 GPa/1815 °C, 2.6 GPa/1865 °C, 4.3 GPa/1990 °C, 4.4 GPa/1950 °C. The results show that the intermediate range ordering of the structure decreases with an increase of both P and T. Based on this study, the carbonate-silicate magmas at upper mantle P-T conditions are expected to increase their viscosities during their ascent through the mantle as a result of increasing intermediate range ordering upon cooling and decompression. Additionally, spectroscopic measurements were carried out on the quenched glasses at ambient pressure using micro-Raman as well as micro-FTIR in reflection and transmission modes in the mid infrared range. High pressure investigation using micro-FTIR was also conducted. The distribution of Qn species obtained by deconvolution of the Raman spectra within the aluminosilicate region confirms the depolymerized nature of the quenched glasses as inferred by the low viscosities of the corresponding liquids; peculiar characteristics of the C vibrations would suggest a distorted environment surrounding the network modifying CO32− anion. No evidence of molecular CO2 was detected. Notably, we find evidence of both dissolved molecular CO and CO linked to a metal cation forming carbonyl complexes in the quenched glasses at P-T-fo2 conditions compatible with a hot Archean upper mantle. This suggests a role for carbonate-silicate magmas as carriers of reduced gaseous C-O-H species towards the early atmosphere along with the mobilization of PGE-elements.