Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite

The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion–mineral interactions during dissolution under far-from-equilibrium conditions remains limited. Here we show that calcite (CaCO3) exhibits a rich array of dissolution features in acidic Pb-bearing solutions. During the initial stage, calcite exhibits nonclassical surface features characterized as micropyramids that developed spontaneously. Subsequent pseudomorphic growth of cerussite (PbCO3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded a cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution–precipitation mechanism. These results show that impurity metal ions exer...