Metastable solubility and local structure of amorphous calcium carbonate (ACC)

Abstract The properties of amorphous calcium carbonate provide the foundation for understanding mineralization of calcified skeletons but inconsistencies between studies suggest the physical picture is incomplete. This study quantifies the metastable solubility and structure of ACC produced under a series of chemical conditions. Using complementary in situ methods that quantify ACC structure (in situ PDF analysis) in parallel with chemical composition (TGA, ICP-OES), we find two short-range structures are produced that also show distinct morphological differences. Conditions with high carbonate ion concentrations stabilize a Ca-rich ACC with short-range order that is independent of Mg content. In contrast, low carbonate solutions favor Mg-rich ACC with mixed Ca- and Mg-short range order. Measurements of solubility product determined from supersaturated and undersaturated conditions find the distinctive structures are related to solution carbonate activity while solubility is primarily determined by the magnesium content of the solid. Bulk solubility is a composite that concurs with established values. The findings demonstrate the type of ACC that forms is tuned by Mg2+ and CO3-2- concentration and suggest ACC structure, not bulk composition, is a reliable indicator of intermediate phase. This chemical framework also provides a basis for interpreting apparent differences between observations of ACC in synthetic and natural systems that reconciles previous structural studies.