Manganese carbonate minerals and their alteration products in Silurian metalliferous nodules from the region of Asaritsa peak, West Balkan Mountain

The studied Silurian nodules have hard light cores and dark shells. The cores consist of quartz with disseminated zonal carbonate mineral and pyrite. Zones in the carbonate have a variable composition from Mn-containing siderite, ankerite and dolomite to mixed Fe-Mn carbonate and Fe-containing rhodochrosite. The nodule shells are composed of quartz, chlorite, sericite, goethite, Mn-Fe oxyhydroxides and siderite. Fe-Mn oxyhydroxides in the nodule shells are formed due to an alteration of the carbonate minerals and inherited their composition. The formation of the nodules with Fe- and Mn-carbonates is related to diagenetic processes under reducing conditions of low Eh and high pH values. Later, carbonate minerals were altered into Fe-Mn oxyhydroxides. These alteration changes can be related to the influence of later magmatic activity in the area. An example of this activity is the presence of an igneous bodies established on both sides of the section.