Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 °C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 °C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite–siderite and dolomite solid solutions. A calcite–siderite solid solution precipitated at 25 °C, with the percentage of CaCO3 in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 °C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature.