TEM study of Pt-C replicas of calcite overgrowths precipitated from electrolyte solutions

The surface microtopography of synthetic magnesian calcite overgrowths on calcite powders was imaged on Pt-C replicas by transmission electron microscopy. The overgrowths were precipitated at room temperature under steady-state conditions from seawater-like solutions, in the presence and absence of Mg2+, SO42-, and PO43- ions, and over a range of saturation states. Overgrowths produced from the Mg-free electrolyte show smooth coverage of the substrate with a few hillocks suggestive of spiral growth. Electrolytes containing Mg consistently produced patchy overgrowths on the {<10(1)over bar 4>} faces of the seed crystals and differential inhibition of growth at their corners and edges. The patchy overgrowths consist of flat-topped islands whose morphology is consistent with two-dimensional surface nucleation rather than spiral growth. The density of islands, their rounding, and their degree of coalescence increased with the saturation state of the precipitating solution. The effect of SO42- on the surface topography was imperceptible. Soluble reactive phosphate (SRP), on the other hand, clearly inhibited growth and dissolution along specific crystallographic directions. The development of irregular surfaces along specific edges and corners of the seed crystals shows that foreign ions promote the development of complex crystal morphology even at high saturation states.