M. Boni, N. Mondillo, G. Balassone, M. Joachimski, A. Colella
Zincian dolomite related to supergene alteration in the Iglesias mining district (SW Sardinia)
International Journal of Earth Sciences, January 2013, Volume 102, Issue 1, pp 61-71.
One of the main effects of supergene alteration of ore-bearing hydrothermal dolomite in areas surrounding secondary zinc orebodies (Calamine-type nonsulfides) in southwestern Sardinia (Italy) is the formation of a broad halo of Zn dolomite. The characteristics of supergene Zn dolomite have been investigated using scanning electron microscopy and qualitative energy-dispersive X-ray spectroscopy, thermodifferential analysis, and stable isotope geochemistry. The supergene Zn dolomite is characterized by variable amounts of Zn, and low contents of Pb and Cd in the crystal lattice. It is generally depleted in Fe and Mn relative to precursor hydrothermal dolomite (Dolomia Geodica), which occurs in two phases (stoichiometric dolomite followed by Fe-Mn-Zn-rich dolomite), well distinct in geochemistry. Mg-rich smithsonite is commonly associated to Zn dolomite. Characterization of Zn-bearing dolomite using differential thermal analysis shows a drop in temperature of the first endothermic reaction of dolomite decomposition with increasing Zn contents in dolomite. The supergene Zn dolomites have higher delta18O but lower delta13C values than hydrothermal dolomite. In comparison with smithsonite-hydrozincite, the supergene Zn dolomites have higher delta18O, but comparable delta13C values. Formation of Zn dolomite from meteoric waters is indicated by low delta13C values, suggesting the influence of soil-gas CO2 in near-surface environments. The replacement of the dolomite host by supergene Zn dolomite is interpreted as part of a multistep process, starting with a progressive "zincitization" of the dolomite crystals, followed by a patchy dedolomitization s.s. and potentially concluded by the complete replacement of dolomite by smithsonite.