Geology, geochemistry, and origin of the continental karst-hosted supergene manganese deposits in the Western Rhodope Massif, Macedonia, Northern Greece

Economic Mn-oxide ore deposits of commercial grade occur in the Rhodope massif near Kato Nevrokopi in the Drama region, Northern Greece. The Mn-oxide mineralization has developed by weathering of continental hypogene rhodochrosite-sulphide veins. The vein mineralization is confined by tectonic shear zones between marble and metapelites, extending laterally into the marble as tabular, pod or lenticular oreshoots (up to 50 m x 20 m x 5-10 m). Supergene oxidation of the hypogene mineralization led to the formation of in-situ residual Mn-oxide ore deposits, and secondary infills of Mn-oxide ore in embryonic and well developed karst cavities. Whole rock geochemical profiles across mineralized zones confirm the role of thrusts and faults as solution passageways and stress the importance of these structures in the development of hydrothermal and supergene mineralization at Kato Nevrokopi. Three zones are recognized in the insitu supergene veins: (A) a stable zone of oxidation, where immobile elements form (or substitute in) stable oxide mineral phases, and mobile elements are leached; (B) a transitional (active) zone in which element behavior is strongly influenced by seasonal fluctuations of the groundwater table and variations in pH-Eh conditions; and (C) a zone of permanent flooding, where variations in pH-Eh conditions are minimal. Zone (B) is considered as the source zone for the karst cavity mineralization. During weathering, meteoric waters, which were CO2-rich (P(CO2) ~10-3.8 to 10-1.4) and oxygenated (fO2 ~10-17 for malachite), percolated downward within the veins, causing breakdown and dissolution of sulfides and marble, and oxidation of rhodochrosite to Mn-oxides. Karst cavity formation was favored by the high permeability along thrust zones. Dissolved Mn2+ was transported into karst cavities in reduced meteoric waters at the beginning of weathering (pH~4.5), and as Mn(HCO3)2 in slightly alkaline groundwaters during advanced weathering (pH~6.8). Mn4+-oxide precipitation took place by fO2 increase in ground waters, or pH increase by continuous hydrolysis and carbonate dissolution. In the well developed karst setting, some mobility of elements occurred during and after karst ore formation in the order Na>K>Mg>Sr>Mn>As>Zn>Ba>Al>Fe>Cu>Cd>Pb.