Co-precipitation and ageing of calcium and zinc carbonates: phase evolution, structural features, and environmental...

The environmental mobility of zinc in contaminated systems is closely related to its incorporation into secondary carbonate phases. In this study, the co-precipitation and ageing of Zn- and Ca-bearing carbonates were investigated under ambient conditions using batch experiments with varying Zn²⁺/Ca²⁺ ratios. Phase evolution was monitored over a period of 30 days through X-ray powder diffraction (XRD), scanning and transmission electron microscopy (SEM, TEM), and energy-dispersive X-ray spectroscopy (EDX). Additionally, geochemical modeling was performed using PHREEQC to assess the thermodynamic plausibility of the observed transformations. The results show that in the presence of Zn, the typical crystallisation sequence of CaCO₃ is significantly altered. Instead of evolving through vaterite, calcite forms directly after mixing of mother aqueous solutions, albeit with poor crystallinity and unusually high Zn incorporation-far beyond the miscibility predicted for the calcite-smithsonite (CaCO₃-ZnCO₃) system (Xu et al., 2023). This metastable Zn-rich calcite is quickly replaced by aragonite, a purer and more0020stable phase, while Zn precipitates predominantly as hydrozincite (Zn₅(CO₃)₂(OH)₆). SEM and TEM observations confirm the nanocrystalline nature and limited internal coherence of hydrozincite, which persists throughout the ageing period. Chemical microanalysis reveals a progressive segregation of Zn and Ca into distinct carbonates: well-crystallised aragonite and poorly crystalline hydrozincite. Although hydrozincite effectively incorporates Zn at early stages, its structural instability and potential solubility raise concerns regarding its long-term retention capacity. These findings contribute to understanding the mechanisms controlling Zn sequestration by carbonate phases and highlight the importance of kinetic and structural factors in determining the persistence and environmental stability of Zn-bearing solids in contaminated waters. ENVIRONMENTAL IMPLICATIONS: This study demonstrates that the presence of Zn significantly alters the crystallisation pathways of calcium carbonates in aqueous environments, with relevant implications for Zn immobilisation and long-term environmental stability. Zn is initially incorporated into poorly crystalline calcite, despite the expected immiscibility between calcite and smithsonite. However, this Zn-rich calcite is transient and structurally unstable, leading to its early dissolution and the release of both Zn and Ca back into the solution. This underscores the importance of considering phase stability, crystallinity, and transformation kinetics when assessing carbonate-mediated Zn immobilisation in natural or engineered remediation systems.