Application of Compositional Techniques in the Field of Crystal Chemistry: A Case Study of Luzonite, a Sn-Bearing Mineral

Out-of-equilibrium crystallization often produces complex compositional variability in minerals, generating zoning and other mixing phenomena. The appropriate microchemical characterization of the resulting out-of-equilibrium patterns is of critical importance in understanding the overall physical and chemical properties of the host crystalline phases. In this framework, the modeling of compositional changes assumes a fundamental role. However, when compositional data are used, their management with standard exploratory, statistical, graphical, and numerical tools may give misleading results attributable to the phenomenon of induced correlations. To avoid these problems, methods able to extract compositional data from their constrained space (the simplex) in order to apply standard statistics, have to be adopted. As an alternative, the use of tools having properties able to work in the simplex geometry has to be considered. A luzonite single crystal (ideal composition, Cu₃AsS₄) exhibiting concentric and sector zoning was studied using electron probe microanalysis in order to understand the mechanisms which give rise to chemical variability and conditions in the developing environment. Compositional variations were determined by collecting data along three different transects. The major and minor elements (Cu, As, S, Fe, Sb, Sn) were analyzed with the aim of characterizing their patterns of association in the crystal and, hence, crystal evolution. The whole covariance structure as well as the chemical relationships between the successive zones was investigated by means of compositional methods, considering both data transformation and the stay in the simplex approach. Results indicate that the crystal grew under quiescent conditions, where chemical control was primarily exercised by the mineral’s surface and only minor effects were due to changes in the composition of the surrounding fluid. Consequently, an oscillatory uptake of chemical components occurred in which a competition between famatinite-like (Cu₃SbS₄) and kuramite-like (Cu₃SnS₄) domains characterized the As-poor zones.