Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

• Published in: Geochimica et cosmochimica acta 2003-10, Vol.67 (20), p.3859-3869
• Main Authors: Prieto, Manuel, Cubillas, Pablo, Fernández-Gonzalez, Ángeles
• Format: Article
• Language: English
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/S0016-7037(03)00309-0

The uptake of Cd 2+ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO 3 solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO 3 solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.