Peter Bačík

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).

Oriented inclusions in apatite in a post-UHP fluid-mediated regime (Tromsø Nappe, Norway)

We report pyrrhotite, anhydrite and dolomite crystal rods in fluorapatite occurring in silicate-bearing carbonate rocks associated with UH P eclogites in the Tromso Nappe of the Scandinavian Caledonides in Norway. The apatite-rich rock (up to 10 vol. %) is composed of Mg-rich calcite-dolomite exsolutions, almandine-grossular garnet, low-jadeite clinopyroxene, magnesiohornblende, phlogopite, and accessory minerals represented mainly by zircon, Fe-Ti oxides and allanite. Fluorapatite occurring as euhedral crystals in the carbonate matrix and as inclusions in garnet and clinopyroxene shows up to 45 mol. % of the hydroxylapatite component, traces of CO 3 2− , probably CN − and small amounts of the britholite and ellestadite components. Pyrrhotite occurs as crystallographically oriented rods parallel to the c axis of the host hydroxyl-bearing fluorapatite either as a dense trellis or in the form of scarce inclusions. Precipitation of pyrrhotite in the fluorapatite was probably facilitated by a volatile sulphur phase ( e.g ., H 2 S), which was enclosed within the apatite nano-channels and interacted with Fe in apatite. Anhydrite and dolomite rods have also been identified in the apatite, pointing to the presence of HCO 3 − in the fluids. The anhydrite is also trapped by exsolved dolomite from calcite in the carbonate matrix. Crystallisation of anhydrite, and probably also the associated pyrrhotite, at about 550–650°C was deduced from calcite–dolomite thermometry. At these amphibolite-facies, post-UH P conditions rapid pyrrhotite precipitation in the host apatite is presumed. Relaxation of the fluorapatite structure in the a -axis direction during decompression facilitated the formation of the oriented inclusions in apatite.

Fluorapatite-hingganite-(Y) coronas as products of fluid-induced xenotime-(Y) breakdown in the Skoddefjellet pegmatite, Svalbard

Abstract The pre-Caledonian NYF Skoddefjellet pegmatite in Wedel Jarlsberg Land, Svalbard, contains xenotime-(Y) that is partly replaced by fluorapatite-hingganite-(Y) reaction coronas. Hingganite-(Y) contains up to 2.0 wt.% of Gd2O3, 4.7 wt.% of Dy2O3, 3.3 wt.% of Er2O3 and 5.5 wt.% of Yb2O3. Such unusual, previously undescribed, xenotime-(Y) breakdown was caused by Ca- and F-bearing fluids interacting with the pegmatite. The occurrence of hinnganite-(Y) as a breakdown product of xenotime-(Y) implies that a Be-bearing phase (beryl in this case) was also involved in the reaction. There are few Ca-bearing primary phases in the pegmatite, indicating that the source of fluid was probably located in the generally Ca-richer host rocks (metasediments), though the fluid composition was modified during metasomatism of the pegmatite (i.e. beryl dissolution).

Provenance of the Permian Malužiná Formation sandstones (Malé Karpaty Mountains, Western Carpathians): evidence of garnet and tourmaline mineral chemistry

Abstract The chemistry of detrital garnets (almandine; spessartine-, grossular-, and pyrope-rich almandine; andradite) and mostly dravitic tourmalines from three sandstone samples of the Permian Malužiná Formation in the northern part of the Malé Karpaty Mts (Western Carpathians, SW Slovakia) reveals a great variability of potential source rocks. They comprise (1) low-grade regionally metamorphosed rocks (metacherts, blue schists, metapelites and metapsammites), (2) contact-thermal metamorphic calcareous rocks (skarns or rodingites), (3) garnet-bearing mica schists and gneisses resulting from the regional metamorphism of argillaceous sediments, (4) amphibolites and metabasic sub-ophiolitic rocks, (5) granulites, (6) Li-poor granites and their associated pegmatites and aplites as well as (7) rhyolites. Consequently, the post-Variscan, rift-related sedimentary basin of the Malužiná Formation originated in the vicinity of a low- to high-grade crystalline basement with granitic rocks. Such lithological types of metamorphic and magmatic rocks are characteristic for the Variscan terranes of the Central Western Carpathians (Tatricum and Veporicum Superunits).

Thermoanalytical investigation of ancient pottery

Ceramic potsherds excavated in Biskupice (Banovce County, Slovakia) dated to the Hallstatt culture (8th to 6th centuries BC) were investigated by TGA, thermodilatometry (TDA) and XRD analysis. It was found that the samples consisted of illite/muscovite, feldspar and quartz. Their thermal behavior was typical for ceramics buried in soil for a long time: the mass loss (∼3 mass%) due to escaping the physically bound water (from room temperature to 300 °C) was followed by a gradual mass loss from dehydroxylation (∼3 mass%) as a consequence of the former rehydroxylation. Above the temperature 800 °C a rapid shrinkage of samples was observed in TDA curves. As follows from these results, maximal firing temperatures did not exceed 800 °C.

Kerimasite, {Ca3}[Zr2]( )O12 garnet from the Vysoká-Zlatno skarn, Štiavnica stratovolcano, Slovakia

Abstract 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.

The Firing Temperature of Romanesque Brick from Pác

Abstract A pavement brick taken from a Romanesque part of the church in Pác, in the Trnava County, Slovakia, was investigated by x-ray diffraction analysis (XRD) and thermal analyses as differential thermal analysis (DTA), thermogravimetry (TG) and thermodilatometry (TD). It was found that the brick contained dehydroxylated illitic clay, calcite and quartz. As revealed, dehydroxylation was completely finished and no redehydroxylation was observed. Partial decomposition of calcite was also found. The estimated firing temperature is between 600 °C and 700 °C.

Influence of milling on physical properties of illite

Raw illitic clay (80 % illite, 4 % montmorillonite, 4 % orthoclase, and 12 % quartz) was milled in a planetary ball mill for 0, 60, 120, and 180 min in air. From milled clay, samples for XRD, granulometry, thermogravimetry, DTA, and dilatometry measurements were prepared. It was found that 1) the phase composition is almost unchanged by milling; 2) the distribution of grain sizes shows two distinct maxima; the ratio of their areas depends on the milling time – longer milling leads to larger agglomerates; 3) the dehydroxylation of illite is a two-step process: the first step is shifted to lower temperatures with the milling time; the temperature of the second step decreases only slightly with the milling time; 4) the mass loss during both steps of the dehydroxylation slightly decreases with the milling time; 5) the onset temperature of sintering sharply decreases at the longest milling time.