The Stabilizing Effect of Silicate on Biogenic and Synthetic Amorphous Calcium Carbonate

Silicate ions increase the thermal stability of the unstable amorphous calcium carbonate (ACC). This effect was observed first by comparing ACC from two different species of cystoliths, small calcified bodies formed in the leaves of some plants. The temperature of crystallization to calcite in the silicate-rich cystoliths from M. alba is 100 degrees C higher than that of the silicate-poor cystoliths from F. microcarpa. The stabilizing effect is confirmed in vitro with synthetic samples differing in their silicate content. With increasing silicate concentration in ACC, the crystallization temperature to calcite also increases. A mechanism of geometric frustration is suggested, whereby the presence of the tetrahedral silicate ion in the flat carbonate lattice prevents organization into crystalline polymorphs.