Mn and Zn incorporation into calcite as a function of chloride aqueous concentration

Abstract

During spiral growth of the calcite rhombohedron {10 1 4}, divalent metals substituting for Ca 2+ are differentially incorporated due to steric differences inherent to the asymmetric kink sites exposed at nonequivalent growth steps. Hence, ions “larger” than Ca 2+ (e.g., Sr 2+ and Ba 2+) exhibit an incorporation trend opposite to that of “smaller” ions (e.g., Mn 2+ and Co 2+). However, Zn 2+ exhibits the same incorporation trend as large ions in coprecipitation experiments conducted from strong NH 4Cl electrolytes. In this study we compared the incorporation trends of Zn and Mn from solutions with various chloride content to test the possibility that the adsorption of “large” ZnCl n 2−n aqueous complexes influences the site preference of Zn. The incorporation trends of Mn and Zn were opposite at the symmetrically nonequivalent growth steps. From a 0.4 M NH 4Cl solution, where Zn aqueous speciation was thermodynamically dominated by the “free” aquo ion, Zn maintained its site preference for the geometrically less constrained surface sites. Thus, Zn exhibits a particular interaction with surface sites and its incorporation trend is not controlled by the prevalence of ZnCl n 2−n complexes. Other factors like the electronic configuration must be considered. The surface microtopography of calcite was found to be sensitive to changes in the aqueous concentrations of NH 4Cl and Zn. Decreases in NH 4Cl concentration resulted in an increase of the density of growth hillocks. The strong adsorbing behaviour of Zn increased the surface roughness, decreased the rate of growth, perturbed the spiral growth mechanism, and triggered the nucleation of discrete surface precipitates (∼0.2 μm) along macrosteps. An increase of Cl incorporation, despite the decrease of its aqueous concentration by dilutions of the parent solution, suggests that surface roughness at the calcite-solution interface is another factor involved in the nonequilibrium process of impurity element incorporation. The significant increase in Mn and Zn incorporation into calcite due to decreases in Cl aqueous concentration demonstrates the role of chloride as an important factor in the partitioning of trace metal ions between calcite and low-temperature aqueous fluids. More importantly, the magnitude of Mn differential incorporation also increased with dilutions which indicates that distribution coefficients commonly calculated from bulk solid analyses may underestimate seriously the surface structural effect imposed on trace element incorporation.