Removal of cadmium from wastewaters by aragonite shells and the influence of other divalent cations

The effect of dissolved Zn, Co, Pb, Mg, and Ca on the uptake of cadmium by biogenic aragonite was investigated. Experiments were performed in batch-reactors using metal-cadmium-bearing solutions and shell fragments with diameters in different ranges, the solid/liquid ratio being 10 grams per liter. Different initial concentrations of cadmium and metals (1.0−0.005 mM) were used. Uptake takes place via heterogeneous nucleation of metal-bearing crystallites onto the shell surfaces. Cadmium removal occurs by surface precipitation of otavite. Under the conditions used here, Co and Ca as well as Pb ≤ 0.3 mM and Zn ≤ 0.3 mM do not have a significant effect on the removal of cadmium. At higher concentrations, Pb and Zn outcompete Cd for the dissolving carbonate ions and thus decrease significantly the Cd removal rates. In contrast, Mg has a slight enhancing effect. Pb and Zn are removed faster than Cd, precipitating as PbCO3, Pb3(CO3)2(OH)2, and Zn5(CO3)2(OH)6. Within 24−72 h, the concentrations of lead, cadmium, and zinc decrease until ∼0.5 μM, and the presence of aragonite buffers the solution to a pH above 8 avoiding redissolution. The study demonstrates the high effectiveness of biogenic aragonite in removing Cd and other metals from polluted waters.