Compressibility and Phase Stability of Iron-Rich Ankerite

The structure of the naturally occurring, iron-rich mineral Ca1.08(6)Mg0.24(2)Fe0.64(4)Mn0.04(1)(CO3)(2) ankerite was studied in a joint experimental and computational study. Synchrotron X-ray powder diffraction measurements up to 20 GPa were complemented by density functional theory calculations. The rhombohedral ankerite structure is stable under compression up to 12 GPa. A third-order Birch-Murnaghan equation of state yields V-0 = 328.2(3) angstrom(3), bulk modulus B-0 = 89(4) GPa, and its first-pressure derivative B'(0) = 5.3(8)-values which are in good agreement with those obtained in our calculations for an ideal CaFe(CO3)(2) ankerite composition. At 12 GPa, the iron-rich ankerite structure undergoes a reversible phase transition that could be a consequence of increasingly non-hydrostatic conditions above 10 GPa. The high-pressure phase could not be characterized. DFT calculations were used to explore the relative stability of several potential high-pressure phases (dolomite-II-, dolomite-III- and dolomite-V-type structures), and suggest that the dolomite-V phase is the thermodynamically stable phase above 5 GPa. A novel high-pressure polymorph more stable than the dolomite-III-type phase for ideal CaFe(CO3)(2) ankerite was also proposed. This high-pressure phase consists of Fe and Ca atoms in sevenfold and ninefold coordination, respectively, while carbonate groups remain in a trigonal planar configuration. This phase could be a candidate structure for dense carbonates in other compositional systems.

Automated summary

A joint experimental and computational study was conducted on the structure of naturally occurring iron-rich mineral ankerite. Results showed that the rhombohedral ankerite structure is stable under compression up to 12 GPa, but undergoes a reversible phase transition at 12 GPa possibly due to non-hydrostatic conditions. DFT calculations suggested a novel high-pressure polymorph with Fe and Ca atoms in different coordinations and carbonate groups remaining in a trigonal planar configuration, which could be a candidate structure for dense carbonates in other compositional systems.