Peculiarities of formation, isomorphism and geochemistry of trace elements of sphalerite and wurtzite unusual varieties from the Goniatite occurrence (Pai-Khoi Ridge, Nenets Autonomous District)

A unique Mn-, Cd-bearing sphalerite from quartz-calcite veins in the coal-bearing series (Visean C1v) marine sediments in a 50 km segment of the middle course of the Silova-Yakha River in the Arctic zone of the European part of Russia (Pai-Khoi Ridge) has been studied. The veins have a conformable and cross-cutting occurrence in two types of rocks: gray limestones and black siliceous-carbonaceous shales, the area is known as the Goniatite occurrence. The sulfide content in vein samples ranges from 0.1 to 2 vol.%. The chemical composition of 27 monomineral samples of Mn-, Cd-bearing sphalerites was studied, 82 points were analyzed. Correlations between typomorphic elements-impurities were revealed and correlation matrix was constructed. Cu, V, Ga, In, Sn, As, Sb, Bi, Pb, Tl, Se, Ag, Au, Ni are positively correlated with each other; Cd, Mn and Ge are negatively correlated with each other. The hydrothermal fluid involved in crystallization of sphalerite is characterized by low temperature (164-211 °С) and average salinity of 5-6 wt.% eq. NaCl. An updated “portrait” of typomorphic features (composition and properties) of sphalerite of the Pai-Khoi province was obtained. The features allowing to determine the type of impurity entering the sphalerite structure – in the form of isomorphic impurity or in the form of microinclusions of paragenetic association minerals – have been established. Submicron inclusions of sulvanite and colusite, invisible by other methods, were detected in sphalerite (by LA-ICP-MS method).The cathodoluminescence data of sphalerite from the Pai-Khoi province were typified. In contrast to other provinces, ZnS crystals here are characterized by almost complete absence of isomorphic iron. This allowed us to study pure isomorphism schemes of ZnS↔MnS, ZnS↔CdS, namely cathodoluminescence and other types of luminescence. The presence of a rare wurtzite-4H polytype in assemblage with sphalerite was revealed. High contents of strategic metals Cd, Ga, In, Ge in the ZnS matrix, as well as sulvanite (V, Cu) in a single paragenesis were found. A serious reassessment of the potential for industrial use of this mineralization will be required.