C2fd20077e 371..386

The carbonate sedimentary record contains diverse compositions and textures that reflect the evolution of oceans and atmospheres through geological time. Efforts to reconstruct paleoenvironmental conditions from these deposits continue to be hindered by the need for process-based models that can explain observed shifts in carbonate chemistry and form. Traditional interpretations assume minerals precipitate and grow by classical ion-by-ion addition processes but are unable to reconcile a number of unusual features contained in Proterozoic carbonates. The realization that diverse organisms produce high Mg carbonate skeletal structures by non-classical pathways involving amorphous intermediates raises the question of whether similar processes are also active in sedimentary environments. This study examines the hypothesis that non-classical pathways to mineralization are the physical basis for some of the carbonate morphologies and compositions observed in natural and laboratory settings. We designed experiments with a series of different solution Mg : Ca ratios and saturation environments to investigate the effects on carbonate phase, Mg content, and morphology. Our observations of diverse carbonate mineral compositions and textures suggest geochemical conditions bias the mineralization pathway by a systematic relationship to Mg : Ca ratio and the abundance of carbonate ions. Environments with low Mg levels produce calcite crystallites with 0–12 mol% MgCO3. In contrast, the combination of high initial Mg : Ca and rapidly increasing saturation opens a non-classical pathway that begins with extensive precipitation of an amorphous calcium carbonate (ACC). This phase slowly transforms to aggregates of very high Mg calcite nanoparticles whose structures and compositions are similar to natural disordered dolomites. The non-classical pathways are favored when the local environment contains sufficient Mg to inhibit calcite growth through increased solubility—a thermodynamic factor, and achieves saturation with respect to ACC on a timescale that is shorter than the rate of aragonite nucleation—a kinetic factor. Aragonite is produced when Mg levels are high but saturation is insufficient for ACC precipitation. The findings provide a physical basis for anecdotal claims that the interplay of kinetic and thermodynamic factors underlies patterns of carbonate precipitation and suggest the need to expand traditional interpretations of geological carbonate formation to include non-classical pathways to mineralization.