Evolution of fluids responsible for iron skarn mineralisation: An example from the Vyhne-Klokoc deposit, Western Carpathians, Slovakia

Abstract

Vyhne-Klokoc, the largest Fe-Skarnn deposit in the Western Carpathians, is related to the emplacement of a large granodiorite pluton in the central zone of a Neogene stratovolcano. Skarn mineralisation is developed in places where apophyses of the pluton intruded basement carbonates. Granodiorite in the apophyses grades into rocks of granitic composition, involving the replacement of mafic minerals and a concomitant decrease in Fe-content. Ca-magnetite exoskarns (not accompanied by endoskarns) developed in three paragenetic stages. Fluid inclusion (Fl) data for quartz in granodiorite suggest the existence of aqueous fluid immiscibility during the early hydrothermal stages. Three end-members of Fis were recognised, with a continuum between all three types. High salinity, liquid-rich, probably secondary Fls (29-68 wt % NaCl eq., Th 450 to 570'C, composed of NaCl+FeCl2+KCl) coexist with vapour-rich Fls with low but variable salt contents (+CO2). Probably late secondary Fls (1-25 wt % NaCl eq., composed mainly of NaCl+CaCl2, Th 188–283°C) form the other end-member type of Fls trapped in granodiorite quartz. Fls from skarn garnets show a large variation in salinity (4-23 wt % NaCl eq., composed of NaCl±FeCl2+CaCl2+ KCl+MgCl2) and Th (220–370°C), independent of the garnet types, probably reflecting variable amounts of magmatic fluids and low salinity meteoric waters. Fls in retrograde quartz, calcite and sphalerite show progressively more dilute (0-4 wt % NaCl eq, Th 215–380°C), probably dominantly meteoric fluids with evidence for boiling at shallow depth. Chlorite crystallisation temperatures, calculated from the chlorite geothermometer, are in good agreement with the Th data for Fls in associated skarn minerals. Compositional changes in the granodiorite apophyses are the result of subsolidus autometasomatic reactions of accumulated saline magmatic fluid inside the apophyses with pre-existing mafic mineral phases. Reactions add the iron to the fluid -the potential source for magnetite skarn. Later mixing with dilute, cooler probably meteoric waters had the effect of decreasing the salinity and density of the equilibrated magmatic fluid, making it more buoyant and capable of moving out from the apophyses into the country rocks, causing metasomatic reactions and precipitating magnetite. An overlap exists between the FI microthermometry data from primary Fls in garnets and late secondary Fls in the granodiorite quartz indicating the same sources of the hydrothermal fluids - probably mixtures of magmatic and meteoric waters. Based on fluid inclusion, geological, petrological and mineralogical data, an integrated fluid evolution model involving magmatic and meteoric fluids is developed to explain the geological and fluid controls on Fe-skarn mineralization associated with granodiorite intrusions. Die Evolution von Fluiden bei Fe-skarn Mineralisation: Ein Beispiel von der Lagerstatte Vyhne-Klokoc, West-Karpathen, Slowakei.