On the mechanism of trace-element uptake during the hydrothermal growth of sulfide mineral crystals

The stable species of cadmium and mercury are formed in iron and lead sulfides at elevated temperatures and pressures under hydrothermal conditions. Their formation proceeds through different mechanisms. The most general mechanism involves the uptake of trace elements in the form of structural species due to isomorphous exchange. The results obtained for cadmium in pyrrhotite indicate that structural defects substantially affect the incorporation of impurities into the crystal structure. It is found that trace elements are accumulated on the surface in the absence of defects and are incorporated into the crystal bulk in the form of structural impurities in the presence of defects. Moreover, at elevated temperatures and pressures, trace elements can form their own (surface nonautonomous) phases. These phases are formed not only at trace-element concentrations close to saturation (Cd in Fe_1.0S) but also under conditions far from saturation as a result of the interaction of trace elements with the oxidized surface of the mineral (the cadmium uptake by galena with the formation of either a sulfate surface phase or a sulfate-chloride surface phase). An important mechanism of trace-element uptake by sulfides during the hydrothermal growth of crystals is associated with external and internal adsorption of impurities by defects. This adsorption manifests itself both in an increase in the content of sorbed mercury in galena at a high sulfur activity due to the interaction of mercury with lead vacancies and in the formation of dislocation cadmium species, which results in an increase in the coefficient of cadmium distribution in the crystal-solution system.