Evolution of borate minerals from contact metamorphic to hydrothermal stages: Ludwigite-group minerals and szaibélyite from the Vysoká – Zlatno skarn, Slovakia

Abstract

Borate minerals of the ludwigite group (LGM) and szaibelyite in association with hydroxylclinohumite, clinochlore, a serpentine mineral, magnesian magnetite, spinel, magnesite, dolomite and sulphide minerals, occur in a magnesian exoskarn in the R-20 borehole located in the Vysoka – Zlatno Cu-Au porphyry-skarn deposit, located within the Stiavnica Neogene stratovolcano, Western Carpathians, central Slovakia. The skarn is developed along the contact of Miocene granodiorite to quartz-diorite porphyry and a Middle-Upper Triassic dolomite-shale-psammite-anhydrite sedimentary sequence. The boron minerals were investigated by electron probe micro-analyser (EPMA) and micro-Raman techniques. The source of boron could have been from the granodiorite/quartz diorite intrusion; however some supply of B from adjacent evaporite-bearing sediments is also possible. Based on textural and compositional data, the minerals originated during two stages. (1) An early high-temperature, contact-metamorphic and metasomatic stage comprises coarse-crystalline aggregate of LGM (types 1 to 3) in association with hydroxylclinohumite, magnetite, and rarely spinel inclusions in LGM. Compositional variations of LGM show a crystallization sequence from early azoproite [≤17 wt% TiO2; ~0.40 atoms pre formula unit (apfu) Ti, which correspond to ≤79 mol% of the Mg2(Mg0.5Ti0.5)O2(BO3) end-member], Ti-Al-rich members of LGM, “aluminoludwigite “[≤14 wt% Al2O3; ≤0.53 apfu, ≤53 mol% of Mg2AlO2(BO3) end-member] and Al-rich ludwigite in the central zone of crystals, to Ti-Al-poor ludwigite in outer parts of crystals. (2) Minerals of the late retrograde serpentinization and hydrothermal stage form irregular veinlets and aggregates, including partial alteration of hydroxylclinohumite to the serpentine-group mineral and clinochlore, replacement of LGM by szaibelyite, formation of the latest generation of Fe-rich, Ti-Al poor ludwigite in veinlets (type 4), and precipitation of dolomite, magnesite and sulphide minerals (valleriite, sphalerite, chalcopyrite). The distinct compositional zoning of the LGM documents a complex evolution of the skarn beginning with a high-temperature stage 1 and ending with a low-temperature overprint, stage 2.