Formation mechanisms and environmental influences on the crystal growth of wulfenite

In this study, we introduce a novel approach using correlative analysis techniques to unravel detailed insights into the environmental influences on crystal growth. Tabular and bipyramidal wulfenite samples from the Mežica mine in north-eastern Slovenia were analysed to combine the morphological aspects of crystal growth with the atomic-resolution reconstruction of the positions of lead (Pb) and molybdenum (Mo) atoms in the parent crystal lattice. These combined data also allow us to present the formation mechanism that enables the development of bipyramidal or tabular morphologies in wulfenite. The bipyramidal and tabular crystals are chemically pure wulfenite (PbMoO₄), as confirmed by various advanced diffraction and spectroscopy techniques. However, each habit includes multiple inclusions, mostly consisting of carbonates, Pb-Fe oxides, Pb oxides and, more rarely, Pb vanadate (descloizite). The differences in the morphologies can be attributed to compositional changes during precipitation from a meteoric solution and thus, we propose a growth mechanism consisting of three different phases of growth. This innovative approach emphasises the importance of understanding the origin of crystal habits, as can help to decipher how external influences can affect the crystal structure and its surface, leading to the dissolution of preferred surfaces and the selective release of Pb and Mo.