Non-competitive and competitive adsorption of Cd²⁺, Ni²⁺, and Cu²⁺ by biogenic vaterite

Ubiquitous bio-minerals exert significant effects on the migration and transformation of metal ions in the environment, however, research into the adsorption of heavy metals by biogenic vaterite (BV) has rarely been reported. The aim of our research was to evaluate the removal effects of Cd²⁺, Ni²⁺, and Cu²⁺ in single and multi-metal ion aqueous solutions using BV induced by Bacillus subtilis. The results demonstrate that the adsorption data of BV for metal ions are more accurately fitted to the Langmuir model compared with the Freundlich model. The max adsorption capacity (mg/g) order of BV was Ni (270.27) > Cu (178.57) > Cd (172.41) in a single-metal system, and Cu (175.44) > Ni (94.34) > Cd (30.30) in a multi-metal system (pH = 5.0, 2.5 g/L). A competitive effect exists amongst heavy metals in multi-metal ion systems, and Cu²⁺ adsorption is less affected by other two ions. Furthermore, BV can maintain favourable adsorption characteristics even in a very strong acidic environment (pH = 3.0), and its adsorptive capability becomes more favourable at higher temperatures. Kinetic analysis shows that the adsorption process can be better described by a pseudo-second-order model. XRD, FTIR, and SEM-EDS results reveal that metal ion adsorption on BV mostly happened through physical means, and the favourable adsorption characteristics of BV might be attributable to its larger specific surface area, aggregated spherical polyporous and organic-inorganic structure.