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Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE–U–Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 μm, usually ≤10 μm in size) in Gd-rich xenotime-(Y) crystals (≤100 μm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates–phosphates. The hydrothermal REE–U–Au mineralisation occurs in a quartz–muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01...)Σ1.01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01...)Σ1.01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I 41/ amd , a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd). [ABSTRACT FROM AUTHOR]

Kerimasite {Ca3}[Zr2](SiFe3+2 )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 skarnporphyry 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 Hf content reported in kerimasite), and small 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 dissolutionreprecipitation. 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 ≈ 700ºC and P ≈ 50-70 MPa. [ABSTRACT FROM AUTHOR]