HypothesisUnderstanding calcium carbonate (CaCO3) precipitation in various polymorphs from nanoparticle size (amorphous calcium carbonate) to microparticle size (vaterite, aragonite, dendrite, calcite) is important for practical applications, including carbon geo-storage (e.g., basalt formations), hydrogen storage, groundwater management, and soil stabilization. Our hypothesis suggests that the interplay of Péclet numbers (Pe), Damköhler numbers (Da), and Supersaturation Index (SI) significantly impacts the evolution of CaCO3 precipitation in fractured porous media in terms of mixing patterns, spatiotemporal evolution, crystal morphology, crystal size, and clogging behavior. ExperimentsThis study takes a novel approach to explore the colloidal formation and precipitation dynamics of CaCO3 within a fractured microfluidic system. Here, calcium chloride (CaCl2) and sodium bicarbonate (NaHCO3) solutions were injected and reacted under varied Pe (0–11), Da (0–1), and SI (2–5). FindingsOur analysis revealed distinct precipitation patterns and mixing types, such as transverse, longitudinal, and incomplete mixing, providing insights into the behavior in fractured porous media. We systematically analyzed the temporal and spatial evolution of precipitation, demonstrating how Pe, Da, and SI dictate precipitation rates and spatial distribution. Additionally, the study uncovered a range of CaCO3 polymorphic forms, illustrating their evolution and coexistence. Morphological changes and crystal sizes were examined to decode nucleation and growth processes. Significantly, our findings highlight the relationship between precipitation and clogging in the fractured medium, offering a deeper understanding of reactive transport in complex porous environments. These insights are crucial for enhancing carbon containment security and storage efficiency in underground formations, improving groundwater remediation techniques, and developing novel construction materials through controlled precipitation processes.