Structural Behavior of Minrecordite Carbonate Mineral upon Compression: Effect of Mg → Zn Chemical Substitution in...

We report the structural behavior and compressibility of minrecordite, a naturally occurring Zn-rich dolomite mineral, determined using diamond-anvil cell synchrotron X-ray diffraction. Our data show that this rhombohedral CaZn_0.52Mg_0.48(CO₃)₂ carbonate exhibits a highly anisotropic behavior, the c axis being 3.3 times more compressible than the a axis. The axial compressibilities and the equation of state are governed by the compression of the [CaO₆] and [ZnO₆] octahedra, which are the cations in larger proportion in each layer. We observe the existence of a dense polymorph above 13.4(3) GPa using Ne as a pressure-transmitting medium, but the onset pressure of the phase transition decreases with the appearance of deviatoric stresses in nonhydrostatic conditions. Our results suggest that the phase transition observed in minrecordite is strain-induced and that the high-pressure polymorph is intimately related to the CaCO₃-II-type structure. A comparison with other dolomite minerals indicates that the transition pressure decreases when the ratio Zn/Mg in the crystal lattice of pure dolomite is larger than 1. Density functional theory (DFT) calculations predict that a distorted CaCO₃-II-type structure is energetically more stable than dolomite-type CaZn(CO₃)₂ above 10 GPa. However, according to our calculations, the most stable structure above this pressure is a dolomite-V-type phase, a polymorph not observed experimentally.