Chemical composition and varieties of fahlore-group minerals from Oligocene mineralization in the Rhodope area, Southern Bulgaria and Northern Greece

Fahlore-group minerals in Oligocene magmatic-hydrothermal deposits from the central and eastern Rhodope area, Bulgaria and Greece (e.g. porphyry-epithermal systems at Pagoni Rachi, Maronia and Kassiteres-Sapes, polymetallic epithermal high- and intermediate-sulfidation veins at Kirki, Perama Hill, Mavrokoryfi, Pefka, Zvezdel-Pcheloyad and Madzharovo, skarn-carbonate replacement deposits at Laki, Davidkovo, Madan, Enyovche and intrusion-related deposits at Kimmeria), cover the whole range of the tetrahedrite-tennantite solid solution series and are dominated by zincian and ferroan varieties reflecting deposition from Zn-(and Fe)-rich fluids. The majority of the studied fahlores are “normal” fully-substituted with Cu (+Ag) close to 10 apfu. However, high-sulfidation epithermal deposits in Greece contain “Cu-excess” tetrahedrite-tennantite; those with extreme high Cu-excess > Fe + Zn occur in transitional high- to intermediate-sulfidation systems, whereas low “Cu-excess” tetrahedrite-tennantite with Zn > Cu-excess + Fe and Fe > Cu-excess + Zn are part of tellurides-bearing intermediate-sulfidation assemblages. The epithermal St. Demetrios and Pefka deposits display the most Cu-rich tetrahedrites (11.039 apfu Cu) and tennantite (11.784 apfu Cu) worldwide. Although Ag substitutes for Cu in the structure of Ag-rich tetrahedrite in several deposits, freibergite with 6.800 apfu Ag occurs only at Mavrokoryfi; in particular, the cadmian freibergite at Mavrokoryfi is the second finding of this variety worldwide. Tellurium-bearing fahlore varieties occur in association with enargite/luzonite and native gold in high-sulfidation ore assemblages. Tetravalent tellurium substitutes for trivalent As and Sb in goldfieldite and Te-rich tennantite and tetrahedrite at Mavrokoryfi, Perama Hill, St. Demetrios and Pefka deposits. Goldfieldite at Mavrokoryfi and Perama Hill is remarkably Te-rich (up to 3.766 apfu and 3.711 apfu Te, respectively), with total metal content of 10.591 apfu and are the closest natural occurrence to the theoretical synthetic endmember Cu10Te4S13. The telluride-bearing fahlores in several epithermal deposits in Greece do not represent decomposition products of early goldfieldite. They are possibly the result of a new influx of Te-rich magmatic volatiles in the system. Decreasing Te (and Cu)-content in tetrahedrite-tennantite solid solution series reflects an evolution from initial high-T, high-sulfidation, oxidizing conditions, towards lower-T and lower-sulfidation, more reduced conditions with time. Fahlores, although they are minor constituents in the studied mineralization types, are carriers of Ag (and Au in goldfieldite) and may be used as an exploration tool, since they are closely associated with either native gold, gold-silver tellurides or Ag-sulfosalts.