Abstract
To investigate the quantitative relationship between the crystal structure and composition of Mn-bearing calcite, the solid solutions of Ca1–xMnxCO3 (x = 0.1, 0.3, 0.5, 0.7, 0.9) with continuous MnCO3 mol% content were synthesized at 1 GPa and 700 °C using high-purity CaCO3 and MnCO3 powders as starting materials. The run products were analysized by electron probe, powder X-ray diffraction and Raman spectroscopy. The CaO wt% and MnO wt% of the resulting products are consistent with the expected compositions. The powder X-ray diffraction results show that the products are single phase without any impurities. All diffraction peaks of samples with varying MnCO3 mol% contents can be indexed by the calcite-type structure carbonates ACO3 (R-3c space group; A is a divalent cation), confirming the previous results that there is the completely continuous solid solution between CaCO3 and MnCO3 end members. The unit-cell parameters and volumes of the solid solutions decrease as the MnCO3 mol% content increases, presenting a linear relationship of Ca–Mn ideal miscibility, which is perfectly consistent with the rigid body model of A-site substitution in ACO3. Besides, as MnCO3 mol% content increases, the bond distance of A–O decreases linearly, while the bond distance of C–O changes like a parabola. Therefore, the addition of Mn makes the bond distance of A–O shorten, resulting in the decrease of unit-cell parameters and volumes for Ca1–xMnxCO3. Furthermore, two exterior vibrations (T and L) of the crystal lattice and two internal vibrations (ν4 and ν1) within the CO32− unit are assigned in the Raman spectra of these solid solutions. The characteristic vibration modes T, L, and ν4 as a whole increase with the increasing of MnCO3 mol% content, whereas the characteristic vibration mode ν1 as a whole decreases with the increase of MnCO3 mol% content. These variations in Raman vibration modes are related to the radius of substituted ions.
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Acknowledgements
We are thankful to Editor Larissa Dobrzhinetskaya and three anonymous reviewers for their valuable comments and advices which helped to improve the manuscript substantially. We also acknowledge Dr. Lin Li for the X-ray diffraction experiments assistance and Dr. Jingui Xu for guiding the full profile-fitting using GSAS software. This project was funded by the National Natural Science Foundation of China (grant nos. 42172048 and U2032118), the Guizhou Provincial Science and Technology Projects (QKHPTRC-YQK[2023]035 and QKHJC-ZK[2021]ZD042), the Hundred Talents Program of the Chinese Academy of Sciences, and the Guizhou Provincial 2020 and 2021 Science and Technology Subsidies (Nos. GZ2020SIG and GZ2021SIG).
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SZ: Synthesize samples, Methodology, Data analysis, Investigation, Writing-original draft, Writing-review and editing, Visualization. WL: Synthesize samples, Investigation, Review and editing, Supervision, Conceptualization. MW: Methodology, Investigation, Visualization. QZ: Methodology, Investigation. DF: Investigation, Review and editing, Supervision, Conceptualization.
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Zhang, S., Liang, W., Wu, M. et al. Crystal structure of calcite-type Ca1–xMnxCO3 solid solution by X-ray diffraction and Raman spectroscopy. Phys Chem Minerals 51, 10 (2024). https://doi.org/10.1007/s00269-024-01269-6
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DOI: https://doi.org/10.1007/s00269-024-01269-6