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Dipositive cation substitution in sulfate minerals has been a topic of investigation both experimentally and computationally. Here the possibility of tripositive cation substitution with accompanying vacancy formation is considered, specifically lanthanum ion substitution in barium sulfate. Experimentally, the lanthanum ions impact “bulk” crystallization in a way that is best explained by considering the solution phase ion-pair interactions. However, morphological results suggest that lanthanum ions do more than impact the free sulfate levels. Atomic force microscopy results showed that both lanthanum and calcium ions are strong inhibitors of barite growth. X-ray diffraction on bulk samples showed that lanthanum ions do indeed incorporate, as determined by lattice parameter changes. Finally, computational modeling suggests that while calcium incorporation is more energetically favorable, lanthanum ions prefer to substitute on the surface more so than calcium ions.

Effect of Lanthanum on the Crystal Growth of Barium Sulfate