From Ions to Crystals: A Comprehensive View of the Non‐Classical Nucleation of Calcium Sulfate

The early stages of mineralization continue to be in the focus of intensive research due to their inherent importance for natural and engineered environments. While numerous observations have been reported for single steps in the pathways of various crystallizing phases in previous studies, the complexity of the underlying processes and their elusive character have left central questions unanswered in most cases. In the present work, we provide a detailed view on the nucleation of calcium sulfate mineralization-an abundant mineral with broad use in construction industry-in aqueous systems at ambient conditions. As experimental basis, a co-titration procedure with potentiometric, turbidimetric and conductometric detection was developed, allowing solution speciation and the formation of crystallization precursors to be monitored quantitatively as the level of nominal (super)saturation gradually increases. The nature and spatiotemporal evolution of these precursors was further elucidated by time-resolved small-angle X-ray scattering (SAXS) and analytical ultracentrifugation (AUC) experiments, complemented by cryogenic transmission electron microscopy (cryo-TEM) as a direct imaging technique. The results reveal how ions associate into nanometric primary species, which subsequently aggregate and develop anisotropic order by intrinsic structural reorganization. Our observations challenge the common understanding of fundamental notions such as the nucleation barrier or the meaning of supersaturation, with broad implications for mineralization phenomena in general and the formation of calcium sulfate in geochemical settings and industrial applications in particular.