Daniel Ozdín

Oxy-schorl, Na(Fe2+2Al)Al6Si6O18(BO3)3(OH)3O, a new mineral from Zlatá Idka, Slovak Republic and Přibyslavice, Czech Republic

Abstract Oxy-schorl (IMA 2011-011), ideally Na(Fe22+Al)Al6Si6O18(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup, is described. In Zlatá Idka, Slovak Republic (type locality), fan-shaped aggregates of greenish black acicular crystals ranging up to 2 cm in size, forming aggregates up to 3.5 cm thick were found in extensively metasomatically altered metarhyolite pyroclastics with Qtz+Ab+Ms. In Přibyslavice, Czech Republic (co-type locality), abundant brownish black subhedral, columnar crystals of oxy-schorl, up to 1 cm in size, arranged in thin layers, or irregular clusters up to 5 cm in diameter, occur in a foliated muscovite-tourmaline orthogneiss associated with Kfs+Ab+Qtz+Ms+Bt+Grt. Oxy-schorl from both localities has a Mohs hardness of 7 with no observable cleavage and parting. The measured and calculated densities are 3.17(2) and 3.208 g/cm3 (Zlatá Idka) and 3.19(1) and 3.198 g/cm3 (Přibyslavice), respectively. In plane-polarized light, oxy-schorl is pleochroic; O = green to bluish-green, E = pale yellowish to nearly colorless (Zlatá Idka) and O = dark grayish-green, E = pale brown (Přibyslavice), uniaxial negative, ω = 1.663(2), ε = 1.641(2) (Zlatá Idka) and ω = 1.662(2), ε = 1.637(2) (Přibyslavice). Oxy-schorl is trigonal, space group R3m, Z = 3, a = 15.916(3) Å, c = 7.107(1) Å, V = 1559.1(4) Å3 (Zlatá Idka) and a = 15.985(1) Å, c = 7.154(1) Å, V = 1583.1(2) Å3 (Přibyslavice). The composition (average of 5 electron microprobe analyses from Zlatá Idka and 5 from Přibyslavice) is (in wt%): SiO2 33.85 (34.57), TiO2 <0.05 (0.72), Al2O3 39.08 (33.55), Fe2O3 not determined (0.61), FeO 11.59 (13.07), MnO <0.06 (0.10), MgO 0.04 (0.74), CaO 0.30 (0.09), Na2O 1.67 (1.76), K2O <0.02 (0.03), F 0.26 (0.56), Cl 0.01 (<0.01), B2O3 (calc.) 10.39 (10.11), H2O (from the crystal-structure refinement) 2.92 (2.72), sum 99.29 (98.41) for Zlatá Idka and Přibyslavice (in parentheses). A combination of EMPA, Mössbauer spectroscopy, and crystal-structure refinement yields empirical formulas (Na0.591Ca0.103□0.306)Σ1.000(Al1.885Fe2+ 1.108Mn0.005Ti0.002)Σ3.000(Al5.428Mg0.572)Σ6.000(Si5.506Al0.494)Σ6.000O18 (BO3)3(OH)3(O0.625OH0.236F0.136Cl0.003)Σ1.000 for Zlatá Idka, and (Na0.586Ca0.017K0.006□0.391)Σ1.000(Fe2+1.879Mn0.015 Al1.013Ti0.093)Σ3.00(Al5.732Mg0.190Fe3+0.078)Σ6.000(Si5.944Al0.056)Σ6.000O18(BO3)3(OH)3(O0.579F0.307OH0.115)Σ1000 for Přibyslavice. Oxy-schorl is derived from schorl end-member by the AlOFe-1(OH)-1 substitution. The studied crystals of oxy-schorl represent two distinct ordering mechanisms: disorder of R2+ and R3+ cations in octahedral sites and all O ordered in the W site (Zlatá Idka), and R2+ and R3+ cations ordered in the Y and Z sites and O disordered in the V and W sites (Přibyslavice).

Sapphires related to alkali basalts from the Cerová Highlands, Western Carpathians (southern Slovakia): composition and origin

Sapphires related to alkali basalts from the Cerová Highlands, Western Carpathians (southern Slovakia): composition and origin Blue, grey-pink and pink sapphires from the Cerová Highlands, Western Carpathians (southern Slovakia) have been studied using CL, LA-ICP-MS, EMPA, and oxygen isotope methods. The sapphire occurs as (1) clastic heavy mineral in the secondary sandy filling of a Pliocene alkali basaltic maar at Hajnáčka, and (2) crystals in a pyroxenebearing syenite/anorthoclasite xenolith of Pleistocene alkali basalt near Gortva. Critical evaluation of compositional diagrams (Fe, Ti, Cr, Ga, Mg contents, Fe/Ti, Cr/Ga, Ga/Mg ratios) suggests a magmatic origin for clastic blue sapphires with lower Cr and Mg, but higher Fe and Ti concentrations in comparison to the grey-pink and pink varietes, as well as similar compositional trends with blue sapphire from the Gortva magmatic xenolith. Moreover, blue sapphires show similar δ18O values: 5.1 ‰ in the Gortva xenolith, 3.8 and 5.85 ‰ in the Hajnáčka placer, closely comparable to mantle to lower crustal magmatic rocks. On the contrary, pink and grey-pink sapphires show higher Cr and Mg, but lower Fe and Ti contents and their composition points to a metamorphic (metasomatic) origin.

Metamorphic vanadian-chromian silicate mineralization in carbon-rich amphibole schists from the Malé Karpaty Mountains, Western Carpathians, Slovakia

Abstract Mineralization, involving vanadian-chromian silicates, has been studied in Lower Paleozoic, carbon-rich amphibole schists with pyrite and pyrrhotite near Pezinok, southwest Slovakia. A detailed electron microprobe study has revealed the presence of V,Cr-rich garnet, clinozoisite, and muscovite, associated with amphiboles (magnesiohornblende, tremolite, actinolite, and edenite), diopside, and albite. The garnet contains 5-19 wt% V2O3, 5-11 wt% Cr2O3, and 2-13 wt% Al2O3 (16-64 mol% goldmanite, 19-36 mol% uvarovite, and 9-59 mol% grossular end-members). The garnet is unzoned or shows V-rich cores and Al-rich rims, or irregular coarse oscillatory zoning with V, Cr, and Al, locally involving Ca and Mn as well. The V,Cr-rich clinozoisite to mukhinite and “chromian clinozoisite” contains 2-9.5 wt% V2O3 and 1.5-11 wt% Cr2O3; the muscovite contains 2.5-8 wt% V2O3 and 0-7 wt% Cr2O3. The mineralization originated from primarily V-, Cr-, and C-rich mafic pyroclastic rocks, affected by volcano-exhalative processes. These rocks were weakly metamorphosed during early Hercynian regional metamorphism (M1), followed by late-Hercynian contact metamorphism (M2) with crystallization of V,Cr-rich silicates, diopside, amphiboles, phlogopite, titanite, albite, quartz, carbonate, pyrite, and pyrrhotite. The youngest Alpine(?) retrograde metamorphic event (M3) is connected with production of V,Cr-poor muscovite, clinochlore, clinozoisite, pumpellyite-(Mg), prehnite, quartz, and carbonates, under prehnite-pumpellite facies conditions.

Schafarzikite from the type locality Pernek (Malé Karpaty Mountains, Slovak Republic) revisited

A rare mineral schafarzikite, an oxide of Fe 2+ and Sb 3+ , was found after more than 80 years at the type locality near Pernek (Male Karpaty Mountains, Slovak Republic). Crystals, druses, and crusts of schafarzikite occur on fractures in quartz-carbonate-stibnite hydrothermal ores. The Sb mineralization is bound to black shales and phyllites in a zone of actinolitic rocks. Associated minerals include ankerite, berthierite, stibnite, valentinite, kermesite, senarmontite, and gypsum. Prismatic crystals of schafarzikite are 0.1–1.0 mm, rarely up to 1.5 mm large, with the dominant forms {110}, {121}, {112}, {010}, {221}, {131}, and {231}. The optical properties are: uniaxial, with relatively strong pleochroism in red-brown tints; refraction indices higher than 1.74; the average refraction index, calculated from the Gladstone-Dale equation, is 2.001. The physical properties of schafarzikite from Pernek are: dark brown to black color, adamantine to metallic luster, brown streak; translucent (brown to orange) in very thin fragments; good {100} cleavage and perfect cleavage along unindexed planes parallel to z axis, tenacity-brittle; VHN10 g micro-hardness = 251 and 278 kp/mm 2 (for two cuts with differing orientation), corresponding to Mohs’ hardness of 3.5–4; calculated density D x = 5.507 g/cm 3 . The electron microprobe analysis gave FeO 19.38, ZnO 0.02, PbO 0.02, Sb 2 O 3 80.36, As 2 O 3 0.55, Bi 2 O 3 0.16, SO 2 0.04, and calculated formula Fe 0.97 (Sb 1.99 As 0.02 )S2.01O 4 . The XRD pattern was indexed in a tetragonal setting, with refined unit-cell parameters are a = 8.6073(2) c = 5.9093(3) A, V = 437.80(2) A 3 , c : a = 0.6865. Thermogravimetric (TG) curve shows mass gain of 1.62 wt. % in the range 20–580 °C, and 5.28 wt. % in the range 580–850 °C caused by Fe 2+ and Sb 3+ oxidation, respectively. The product of TG analysis is a phase isostructural with rutile. A tentative assignment of FTIR and Raman spectra of schafarzikite is given. Schafarzikite from Pernek most likely crystallized from late oxidizing hydrothermal fluids. Hence, it is not a weathering product, as assumed previously.

Chovanite, Pb15−2xSb14+2xS36Ox (x ~ 0.2), a new sulphosalt species from the Low Tatra Mountains, Western Carpathians, Slovakia

Chovanite, a new representative of the group of oxysulphosalts of Pb and Sb was found in three hydrothermal deposits of antimony ore, Dubrava, Male ´ ˇ Zelezne ´, and Klacianka, situated on the northern slopes of the Low Tatra Mountains, Slovakia. It is associated with other Pb-Sb sulphosalts, especially boulangerite, robinsonite and dadsonite. In reflected light, chovanite is white, bireflectance is distinct already in air. Pleochroism is present; colour varies from white with a yellowish green tint (darkest position) to white with a faint bluish tint (lightest position). Reflectance values in air are Rmax -R min (%) (l nm): 43.6-37.7 (470), 43.0-36.7 (546), 41.3-35.4 (589), 39.2-34.0 (650). Anisotropy is moderate to strong both in air and in oil, with blue grey to brown grey polarization colours. Internal reflections and twinning are absent. The optical properties are very similar to boulangerite. Micro-indentation hardness is 222.5 with a range 213-238. Derived Mohs hardness is 3. Cleavage is good, parallel to the c axis. Simplified chemical formula based on electron-microprobe analyses is Pb14.42(35)Sb14.33(11)S36.04(23), Z ¼ 4, which corresponds to Pb 50.74, Sb 29.63, S 19.62, total 100.00 wt%. No other elements exceed detection limits; chlorine is absent and oxygen was not measured. Structural formula is Pb15-2xSb14þ2xS36Ox (Z ¼ 4) for which the above mean of microprobe measurement data and the structure refinement give the value of x equal to � 0.2. Density (calc.) is 7.14 g/cm 3 . Crystal system is monoclinic, space group C2/m, lattice parameters a ¼ 48.189(48) A ˚ , b ¼ 4.1104(40) A ˚ , c ¼ 34.235(35) A ˚ , b ¼ 106.059(15) � , V ¼ 6517(11) A ˚ 3 , Z ¼ 4. Chovanite belongs to a sulphosalt family of boxwork structures, together with pellouxite, scainiite, pillaite, marruccite, vurroite, neyite, and several synthetic sulphosalts. Its crystal structure contains 11 independent lead sites, 13 coordination polyhedra of antimony, some of them with Sb sites split into two partially occupied non-overlapping positions, and five mixed Pb, Sb sites. The boxwork structure of chovanite is formed by a combination of three types of structural modules: (a) continuous walls with a complex structure of rod-layer type; these walls are interconnected by (b) rod-like partitions, and the resulting box-like channels (c) are filled by still another type of structure rods. Chovanite has the largest box-like channel system and infill elements known at present. In spite of differences in chemical composition, chovanite is structurally closest to pellouxite (Cu,Ag)2Pb21Sb23S55ClO which has a moderately large boxwork channel system.

Alpine oxidation of lithium micas in Permian S-type granites(Gemeric unit, Western Carpathians, Slovakia)

Abstract Lithium micas of the zinnwaldite and phengite-Li-phengite series occur as characteristic minerals in Permian Li-F-(P) granites of the western Gemeric unit (Western Carpathians) accompanied by topaz, tourmaline, Nb, Ta, Ti, Sn oxides and aluminophosphates. The calculated Li2O contents of all the mica analysed, together with Rb2O and Cs2O were confirmed by LA-ICP-MS analyses for all the identified micas. Samples from three localities were investigated: two surficial (Surovec, Vrchsúl’ová); and one drill hole (Dlhá dolina). Zinnwaldite (polylithionite) occurs in the upper level of the Dlhá dolina granitic intrusion and in the nearby shallow satellite body of Surovec. The lower level porphyritic granites contain only siderophyllite. The Vrchsú l’ová micas are closer in composition to Li-annite and siderophyllite. Dioctahedral micas are mostly phengites, although zinnwaldite-bearing granites are rich in late-crystallizing Li-phengite, which extensively replaces earlier zinnwaldite. The secondary Liphengite and phengite are interpreted as products of Alpine metamorphism during Cretaceous burial and subsequent exhumation of the Gemeric unit. Reactions are suggested explaining the formation of Li-phengite by reaction of zinnwaldite with phengite or with muscovite. All mica types were investigated by Mössbauer spectroscopy, which showed high degrees of oxidation (25-50% Fe3+ of total Fe) with the exception of zinnwaldite from Vrchsú l’ová, which may have preserved an original, reduced value of 10%. The metamorphic assemblage present permitted calculation of P-T-X conditions: T = 184°C, P = 320 MPa, with oxidation of siderophyllite to phengite + goethite and fO2 at DNN = 4.7, confirming the low-grade conditions of the Alpine metamorphism in agreement with previous estimates.