Crystal-Chemical and Spectroscopic Study of Gem Sphalerite from Banská Štiavnica, Slovakia

Abstract

A complex crystal-chemical investigation based on spectroscopic methods, Electron MicroProbe Analysis (EMPA), and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was made on sphalerite samples from the Terézia and Rozália veins in the Banská Štiavnica ore district. The yellow (sample A) and olive-green sphalerite (C) are in association only with quartz; orange sphalerite (B) is associated with quartz and chalcopyrite; and black sphalerite (D) is associated with galena, chalcopyrite, quartz, and baryte. EMPA revealed that Cd and Fe are substituting for Zn with variable proportions; the Cd/Fe ratio decreases from 2.82–2.85 in the A sample to 0.42 in the D sample. LA-ICP-MS showed that, except Cd and Fe, only Mn has content above 20; Co and Cu vary between 2 and 17 ppm. The optical absorption spectra exhibit absorption between 644 and 740 nm with three smaller humps at 669–671, 698–702, and 732–743 nm, and weaker absorption bands at 858–894 nm in the NIR region, which can be all assigned to crystal-field transitions of Fe2+. The absorption edge starts at about 600 nm to the UV region. Minimal absorption is in the yellow-red part of the visible spectrum giving rise to yellowish-orange and orange-red colors. Absorption in the red region for olive-green sphalerite is more pronounced, explaining the shift to greenish hues. In black sphalerite, the absorption pattern is similar to the olive-green sphalerite, but the bands in the 644 to 740 nm region are less defined. The black color could be caused by slightly higher concentrations of Fe, the smaller size of individual crystals in the aggregate reducing macroscopic transparency, and/or the presence of submicroscopic inclusions.