Abstract
The structural parameters and the thermal behavior of a complete series of Ca–Mg carbonates synthesized at high pressure and temperature (1–1.5 GPa, 1273–1373 K) in the range 0–50 mol% MgCO3 have been investigated by in situ powder synchrotron high-resolution X-ray diffraction at ambient and up to 1073 K under self-controlled CO2 partial pressure. The crystal structures are disordered Mg calcite in the range 1–41 mol% MgCO3, and Ca dolomite at 49 mol% MgCO3. New calibration curves of the cell parameters for the Mg content and thermal expansion from ambient to 1073 K are given. Short-range structural effects of cation substitution and ordering and their thermal behavior as a function of Mg content were identified from three sets of data: the peak broadening, the cell parameter strains and the Raman band enlargements. Both intra- and inter-crystalline levels of compositional heterogeneity are identified and allow splitting the Mg calcites into two groups: low- and high-Mg calcites. The low-Mg calcites (up to 22 mol% MgCO3) are homogeneous in Mg content with short-range ordering. High-Mg calcite (up to 41 mol% MgCO3) displays domains with different local ordering configurations and similar or slightly different Mg contents, and to which is added a compositional variation between crystals, as determined by EMP, of the order of ± 0.8 mol% MgCO3. The cation ordering in Ca-rich dolomites similarly occurs in high-Mg synthetic calcites. The role of (CO3)2− group ordering is shown to be an important factor in the formation of Ca–Mg carbonates.
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Acknowledgements
This work has been supported by the Centre National de la Recherche Scientifique (CNRS)—Institut National des Sciences de l'Univers (INSU) through grant INTERRVIE 2017 to DV, by the Agence Nationale pour la Recherche through ANR MOBi 2018, and by the Centre Interdisciplinaire de Nanoscience de Marseille (CINaM) through internal grants. We would like to thank A. Saùl and A. Ricolleau for constructive discussions. This is contribution ANR MOBi 2. We are grateful to the European Synchrotron Radiation Facility for providing access to the instruments and we would like to thank Andy Fitch for assistance in using beamline ID22.
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Floquet, N., Vielzeuf, D., Heresanu, V. et al. Synchrotron high-resolution XRD and thermal expansion of synthetic Mg calcites. Phys Chem Minerals 47, 48 (2020). https://doi.org/10.1007/s00269-020-01115-5
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DOI: https://doi.org/10.1007/s00269-020-01115-5