Huang Y.-CRao AHuang S.-JChang C.-YDrechsler MKnaus JCHUN-CHUNG CHANRaiteri PGale J.DGebauer D.2022-04-252022-04-25202114337851https://www.scopus.com/inward/record.uri?eid=2-s2.0-85108189648&doi=10.1002%2fanie.202104002&partnerID=40&md5=ea16dbe08546a4055b619c11afe23de5https://scholars.lib.ntu.edu.tw/handle/123456789/606867Mechanistic pathways relevant to mineralization are not well-understood fundamentally, let alone in the context of their biological and geological environments. Through quantitative analysis of ion association at near-neutral pH, we identify the involvement of HCO3? ions in CaCO3 nucleation. Incorporation of HCO3? ions into the structure of amorphous intermediates is corroborated by solid-state nuclear magnetic resonance spectroscopy, complemented by quantum mechanical calculations and molecular dynamics simulations. We identify the roles of HCO3? ions as being through (i) competition for ion association during the formation of ion pairs and ion clusters prior to nucleation and (ii) incorporation as a significant structural component of amorphous mineral particles. The roles of HCO3? ions as active soluble species and structural constituents in CaCO3 formation are of fundamental importance and provide a basis for a better understanding of physiological and geological mineralization. ? 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbHamorphous materialsbicarbonatecalcium carbonatemineral nucleationNMR spectroscopyCalciteCalcium carbonateCarbonate mineralsCrystallizationGeologyMineralogyMolecular dynamicsNuclear magnetic resonance spectroscopyNucleationQuantum theoryAmorphous mineralsCalcium carbonate formationGeological environmentMechanistic pathwaysMolecular dynamics simulationsQuantum-mechanical calculationSolid state nuclear magnetic resonance spectroscopyStructural componentIons[SDGs]SDG13journal article10.1002/anie.202104002339736912-s2.0-85108189648