The effect of stoichiometry on the new formation and subsequent growth of CaCO3 was investigated over a large range of solutionstoichiometries (10–4 < raq < 104, where raq = {Ca2+}:{CO 32–}) at various, initially constant degrees of supersaturation (30 < Ωcal < 200, where Ωcal = {Ca2+}{CO32–}/Ksp), pHof 10.5 ± 0.27, and ambient temperature and pressure. At r aq = 1 and Ωcal < 150, dynamic light scattering (DLS) showed that ion adsorption onto nuclei (1–10 nm) was the dominant mechanism. At higher supersaturation levels, no continuum of particle sizes is observed with time, suggesting aggregation of prenucleation clustersinto larger particles as the dominant growth mechanism. At r aq ≠ 1 (Ωcal = 100), prenucleation particles remained smaller than 10 nm for up to 15 h. Cross-polarized light in optical light microscopy was used to measure the time needed for new particle formation and growth to at least 20 μm. This precipitation time depends strongly and asymmetrically on raq. Complementary molecular dynamics(MD) simulations confirm that raq affects CaCO3 nanoparticle formation substantially. At r aq = 1 and Ωcal ≫ 1000, the largest nanoparticle in the system had a 21–68% larger gyration radius after 20 ns of simulationtime than in nonstoichiometric systems. Our results imply that, besides Ω cal, stoichiometry affects particle size, persistence, growth time, and ripening time toward micrometer-sized crystals. Our results mayhelp us to improve the understanding, prediction, and formation of CaCO 3 in geological, industrial, and geo-engineering settings.
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