Experimental investigation of calcium carbonate mineralogy in past and future oceans

Inorganic marine calcium carbonate formation and mineralogy varies significantly concurrent with the solution composition. During the Phanerozoic, due to oscillations in the seawater composition, this resulted in the formation of either dominantly calcite or aragonite. Variations in seawater composition also appear to have influenced the evolution of biomineralizing organisms. Additionally, many organisms utilize amorphous calcium carbonate (ACC) during biomineralization. The occurrence of calcite and aragonite throughout the Phanerozoic and calcium carbonate biomineralization were investigated. This was done by determining the influence of solution chemistry (SO4 and Mg) on calcium carbonate formation, mineralogy and stability via a variety of laboratory and synchrotron based synthesis experiments. During the formation of aragonite and calcite, aqueous SO4 and the Mg/Ca ratio both affect the formation of calcite and aragonite. An increase in aqueous SO4 decreases the Mg/Ca ratio at which calcite is destabilized and aragonite becomes dominant. These results suggest that the models relating seawater chemistry to calcium carbonate formation needs re-evaluation. Abiotic ACC crystallization to vaterite occurs in three stages. In the first stage, ACC crystallizes to vaterite via a spherulitic growth mechanism. The second stage is characterized by surface particle growth at the expense of ACC. Finally, particle growth via Ostwald ripening is the only remaining process. This process can be described as the inorganic analogue to biological ACC crystallization, which is adjusted by organisms to produce their preferred calcium carbonate polymorph and morphology. An increase in SO4 concentration only decreases the spherulitic growth rate and Ostwald ripening, even when rapidcreekite (as an intermediate) and gypsum crystallizes. Finally, SO4 promotes the formation of vaterite. Depending on the formation process this is caused by either the stabilization of vaterite and destabilization of calcite (slow heterogeneous formation), or by the destabilization and inhibition of calcite formation (spherulitic growth).