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Free keywords:
deep carbon cycle, calcium carbonate, solid solution, phase diagram, phase transition, high pressure, vibrational spectroscopy
Abstract:
The high-pressure CaCO3 phase diagram has been the most extensively studied within the carbonates group. However, both the diverse mineralogy of carbonates and the abundance of solid solutions in natural samples require the investigation of multi-component systems at high pressures (P) and temperatures (T). Here we studied a member of the CaCO3–SrCO3 solid solution series, and revealed the effect of substituting Ca2+ with Sr2+ on the pressure-induced phase transitions in calcium carbonate.
A synthetic solid solution Ca0.82Sr0.18CO3 was studied in situ by Raman spectroscopy in a diamond anvil cell (DAC) up to 55 GPa and 800K. The results of this work show significant differences in the high-pressure structural and vibrational behavior of the (Ca, Sr)CO3 solid solution compared to that of pure CaCO3. The monoclinic CaCO3-II-type structure (Sr calcite-II) was observed already at ambient conditions instead of the ‘expected’ rhombohedral calcite. The stress-induced phase transition to a new high-pressure modification, termed here as Sr-calcite-IIIc, was detected at 7GPa. Sr-calcite-VII formed already at 16GPa and room T, which is 14GPa lower compared to CaCO3-VII. Finally, crystallization of Sr-aragonite was detected at 540K and 9GPa, at 200K lower T than pure aragonite. Our results indicate that substitution of Ca2+ by bigger cations, such as Sr2+, in CaCO3 structures can stabilize phases with larger cation coordination sites (e.g. aragonite, CaCO3-VII, and post-aragonite) at lower P –T conditions compared to pure CaCO3. The present study shows that the role of cationic composition in the phase behavior of carbonates at high pressures should be carefully considered when modeling the deep carbon cycle and mantle processes involving carbonates, such as metasomatism, deep mantle melting,and diamond formation.
