Abstract

Kerimasite {Ca3}[Zr2](SiFe23+)O12, a rare member of the garnet supergroup, has been identified in association with andradite–grossular and their hydrated analogues, monticellite, perovskite, clintonite, anhydrite, hydroxylellestadite–fluorellestadite, spinel, magnetite, brucite, valeriite and other minerals from a Ca-Mg skarn in the exocontact of a granodiorite porphyry intrusion in Vysoká-Zlatno Cu-Au skarn-porphyry deposit, the Štiavnica stratovolcano, Central Slovakia. Kerimasite forms euhedral-to-anhedral crystals, 2 to 100 μm across with 0.73–1.62 atoms per formula unit (a.p.f.u.) Zr (16.2–33.6 wt.% ZrO2), 0.34–0.66 a.p.f.u. Ti (4.6–9.3 wt.% TiO2), 0.01 to 0.05 a.p.f.u. Hf (0.4–1.7 wt.% HfO2: the largest content reported in kerimasite), and small Hf amounts of Sn, Sc and Nb (≤0.02 a.p.f.u.). Tetrahedral Si (0.99–1.67 a.p.f.u.; 9.8–18.1 wt.% SiO2) is balanced by 0.85–1.26 a.p.f.u. Fe3+ and by 0.46–0.76 a.p.f.u. Al. The crystals commonly show regular, oscillatory concentric zoning or irregular patchy internal textures due to Zr, Ti, Fe, Al and Si variations during growth or partial alteration and dissolution-reprecipitation. The main substitutions in kerimasite are Y(Fe,Sc)3+ + ZSi4+ = Y(Zr,Ti,Hf,Sn)4+ + Z(Fe,Al)3+ and Ti4+ = Zr4+. Associated andradite locally contains irregular Ti- and Zr-rich zones with ≤11 wt.% TiO2 and ≤4.4 wt.% ZrO2. In comparison with common Ca-rich garnets, the micro-Raman spectrum of kerimasite shows that many bands shift towards much lower wavenumbers, either due to Fe3+ substitution on the Z site or to the strong influence of neighbouring octahedrally-coordinated Zr4+ on internal vibrations of tetrahedra that share oxygens. The formation of kerimasite, monticellite, perovskite and other phases indicate a relatively Ca-rich and Si,Al-poor environment, analogous to other known occurrences of Ca-Zr garnets (Ca-rich skarns and xenoliths, carbonatites). Kerimasite and associated skarn minerals originated during contact-thermal metamorphism of Upper Triassic marl slates with limestone, dolomite, anhydrite and gypsum by Miocene granodiorite porphyry at T ≈ 700°C and P ≈ 50–70 MPa.

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