Milan Novák

Nomenclature of the tourmaline-supergroup minerals

Abstract A nomenclature for tourmaline-supergroup minerals is based on chemical systematics using the generalized tourmaline structural formula: XY3Z6(T6O18)(BO3)3V3W, where the most common ions (or vacancy) at each site are X = Na1+, Ca2+, K1+, and vacancy; Y = Fe2+, Mg2+, Mn2+, Al3+, Li1+, Fe3+, and Cr3+; Z = Al3+, Fe3+, Mg2+, and Cr3+; T = Si4+, Al3+, and B3+; B = B3+; V = OH1- and O2-; and W = OH1-, F1-, and O2-. Most compositional variability occurs at the X, Y, Z, W, and V sites. Tourmaline species are defined in accordance with the dominant-valency rule such that in a relevant site the dominant ion of the dominant valence state is used for the basis of nomenclature. Tourmaline can be divided into several groups and subgroups. The primary groups are based on occupancy of the X site, which yields alkali, calcic, or X-vacant groups. Because each of these groups involves cations (or vacancy) with a different charge, coupled substitutions are required to relate the compositions of the groups. Within each group, there are several subgroups related by heterovalent coupled substitutions. If there is more than one tourmaline species within a subgroup, they are related by homovalent substitutions. Additionally, the following considerations are made. (1) In tourmaline-supergroup minerals dominated by either OH1- or F1- at the W site, the OH1--dominant species is considered the reference root composition for that root name: e.g., dravite. (2) For a tourmaline composition that has most of the chemical characteristics of a root composition, but is dominated by other cations or anions at one or more sites, the mineral species is designated by the root name plus prefix modifiers, e.g., fluor-dravite. (3) If there are multiple prefixes, they should be arranged in the order occurring in the structural formula, e.g., “potassium-fluor-dravite.”

Schorl-oxy-schorl to dravite-oxy-dravite tourmaline from granitic pegmatites; examples from the Moldanubicum, Czech Republic

Wet-chemical analyses (41) of tourmaline from granitic pegmatites (barren, barren-pocket, beryl, lepidolite types) in the Moldanubicum, Czech Republic revealed that members of the oxy-subgroup ĄV common oxy-schorl, minor oxy-dravite and rare oxy-foitite are more abundant relative to the relevant members of the hydroxy-subgroup. The primary substitution mechanisms in tourmaline show combination of heterovalent substitutions: YAlWO YR2+-1W(OH)-1, XďYAl2WO XNa-1YR2+-2W(OH)-1, XďYAl XNa-1YR2+-1 and Xď W(OH) XNa-1WO-1, and homovalent substitutions: Fe2+Mg-1 and (OH)F-1. Tourmalines with the chemistry expressed by the general formula X(Na0.5ď0.5)Y(R2+2Al)ZAl6(BO3)3Si6O18V(OH)3W(O0.5OH0.5) crystallized in very similar PT conditions in granitic systems saturated on Na, Al, Si and H2O, it indicates the importance of short-range order requirements on tourmaline chemical composition. Abundance of heterovalent substitutions involving the W-site requires determination of light elements (H, B, F, Li) and Fe2+/Fe3+ in tourmalines to specify substitution mechanisms with certainty. Normalization of electron-microprobe data of (Fe,Mg)-rich, (Ca,Li,F)-poor tourmalines from granitic pegmatites on (OH,F)3.5O0.5, which is more probable than (OH,F)4, seems to be suitable.

Elbaite pegmatites in the Moldanubicum: a new subtype of the rare-element class

SummaryA new subtype of complex rare-element granitic pegmatites, the elbaite subtype, is proposed to designate pegmatites in which most of Li is stored in tourmaline. Elbaite pegmatites are widespread in the Bohemian and Moravian parts of the Moldanubicum. Internal structure commonly is simple, progressing from a granitic border unit through a graphic unit to local pods of blocky K-feldspar. Patches of an albitic unit are associated with the blocky pods or pockets developed in the central parts of some dikes. A very low proportion of micas is typical. Tourmaline (schorl to elbaite) is an omnipresent subordinate to accessory phase. Elbaite is found at and within the pockets, or associated with albite ± lepidolite in massive pegmatite. Hambergite, danburite, datolite and boromuscovite have been found at some localities. Elbaite from the elbaite pegmatites is apparently enriched in Mn and F, and shows low vacancies in the X-site, relative to elbaite from the lepidolite subtype. Lepidolite from elbaite pegmatites is close to polylithionite, whereas lithium micas from pegmatites of the lepidolite subtype show highly variable compositions from lithian muscovite to lepidolite with a substantial amount of the trilithionite (up to polylithionite) component.Paragenesis and composition of the elbaite pegmatites indicate conditions of consolidation that are rather different from those of other subtypes of the complex pegmatites: high activity of B, increased alkalinity of the parent medium, and reduced activity of P.ZusammenfassungUm Pegmatite zu kennzeichen, in denen Li hauptsächlich an Li-führende Turmaline gebunden ist, wird ein Elbait Subtyp komplexer granitischer Selten-Element Pegmatite vorgeschlagen. Zusammen mit dem häufigeren und üblicherweise stärker Li-angereicherten Lepidolith-Subtyp, sind Elbait-Pegmatite im Moldanubikum Böhmens und Mährens weitverbreitet. Die Internstruktur ist allgemein einfach, beginnend mit einer granitischen Randzone, gefolgt von einer schriftgranitischen Zone mit Nestern mit blockigem K-Feldspat. Albit-reiche Zonen die sich im zentralen Teil der Pegmatitgänge entwickelten, sind mit diesen Nestern verbunden. Ein geringer Glimmeranteil ist typisch. Turmalin (Schörl bis Elbait) ist untergeordnet bis akzessorisch allgegenwärtig. Elbait kommt in den Taschen, oder vergesellschaftet mit Albit ± Lepidolith in den massigen Pegmatiten vor. Hambergit, Danburit, Datolith und Boromuscovit sind gelegentlich gefunden worden. Sie stellen späte Drusen-Minerale dar. Der Elbait aus den Elbait-Pegmatiten ist an Mn und F angereichert, und zeigt im Vergleich zum Elbait aus dem Lepidolith-Subtyp, wenig Leerstellen auf den X-Positionen. Lepidolith aus Elbait-Pegmatiten ähnelt Polylithionit, während Li-Glimmer aus Pegmatiten des Lepidolith-Subtyps sehr variable Zusammensetzungen von Li-betontem Muscovit bis Lepidolith mit erheblichen Anteilen von Trilithionit (bis Polylithionit) enthalten.Die Paragenese und Zusammensetzung der Elbait-Pegmatite verweisen auf Bildungsbedingungen, die sich erheblich von denen anderer Subtypen komplexer Pegmatite unterscheiden. hohe B-Aktivität, erhöhte Alkalinität der Fluidphase und niedrige P-Aktivität.

Extreme variation and apparent reversal of Nb-Ta fractionation in columbite-group minerals from the Scheibengraben beryl-columbite granitic pegmatite, Maršíkov, Czech Republic

Compositional variation in columbite-group minerals was studied from the beryl-columbite pegmatite at Scheibengraben, Marsikov, Northern Moravia, Czech Republic. The pegmatite consists of five textural-paragenetic units, from the least to the most evolved: volumetrically dominant coarse-grained unit, subordinate graphic and blocky units and a minor cleavelandite unit. Saccharoidal albite unit is rather randomly distributed within the dike. It replaces and/or crosscuts all other units except the cleavelandite unit. Columbite-group minerals are the dominant Nb,Ta-oxide phases in all units. They are associated with other Nb,Ta-oxide minerals: minerals of the pyrochlore subgroup and fersmite in the coarse-grained unit, and minerals of the microlite subgroup, ferrotapiolite and rynersonite in the cleavelandite unit. The extreme Nb-Ta [Ta/(Ta+Nb) = 0.06 to 0.97 (microlite 0.99)] and appreciable Fe-Mn [Mn/(Mn+Fe) = (ferrotapiolite 0.22) 0.35 to 0.90] fractionations in columbite-group minerals differ from those observed in beryl pegmatites examined to date, but they are comparable with those in some highly fractionated, complex, Li-rich pegmatites. High activity of F (facilitated by low contents of B, P and Li in the pegmatite melt) very likely maximized such an extensive Nb-Ta fractionation, over and above differential solubilities of columbite and tantalite in pegmatite melt. The apparent reversal of Nb-Ta and Fe-Mn fractionation found in columbite from the saccharoidal albite unit seems to be an artefact from early units (particularly the coarse-grained one), which were extensively replaced by saccharoidal albite.

Rossmanite, ⃞(LiAl2)Al6(Si6O18)(BO3)3(OH)4, a new alkali-deficient tourmaline: Description and crystal structure

Abstract Rossmanite is a new tourmaline species from near Rožná, western Moravia, Czech Republic. It forms pale pink columnar crystals about 25 mm long and 5 mm thick, elongaten along c with striations parallel to c on the prism faces. It is brittle, H= 7, Dmeas = 3.00 g/cm3, Dcalc = 3.06 g/cm3. In plane-polarized light, it is colorless. Rossmanite is uniaxial negative, to = 1.645(1), e = 1.624(1), trigonal, space group R3m, in the hexagonal setting a = 15.770(2), c = 7.085(1) Å, V = 1525.8(4) Å3, Z= 3. The strongest six X-ray diffraction lines in the powder pattern are at d = 3.950 Å with I = 100% for (hkl) = (220); 2.552 Å, 93%, (051); 1.898 Å, 72%, (342); 4.181 Å, 58%, (211); 2.924 Å, 56%, (122); and 3.434 Å, 53%, (012). Analysis by a combination of electron microprobe, SIMS, H-line extraction, and crystal-structure refinement gave SiO2 38.10 wt%, Al2O3 44.60, Na2O 1.43, Li2O = 1.13, B2O3 = 10.88, H2O = 3.70, F = 0.20, O ≡ F 0.08, sum = 99.96 wt%, Fe, Mg, Ca, Mn, Ti, F, K not detected. The formula unit (31 anions) is x(⃞57Na0.43)Y(Li0.71Al2.17)zAl6(Si5.92O18) (B2.92O9)(OH)3.83F0.10O0.07, with the ideal end-member formula ⃞(LiAl2)Al6(Si6O18)(BO3)3(OH)4; thus rossmanite can be derived from elbaite [Na(Al1.5Li1.5)(Si6O18)(BO3)3(OH)4] by the substitution x⃞2 + YAl → xNa2 + YLi, where ⃞ = vacancy. The crystal structure of rossmanite was refined to an R index of 1.7% using 1094 observed (5σ) reflections collected with MoKα X-radiation from a single crystal. The structure refinement confirmed the low occupancy of the X site and the presence of Li at the Y site. There is considerable positional disorder at the O1 and O2 sites induced by the local variations in bond-valence distribution associated with ⃞-Na disorder at X and Li-Al disorder at Y.

The Al (Nb, Ta) Ti(in−2) substitution in titanite: the emergence of a new species?

SummaryThe highest (Nb, Ta) content ever encountered in titanite is reported from the Maršíkov 11 pegmatite in northern Moravia, Czech Republic. This dike is a member of a pegmatite swarm of the beryl-columbite subtype, metamorphosed under conditions of the amphibolite facies. The pegmatite carries, i.a., rare tantalian rutile intergrown with titanian ixiolite, titanian columbite-tantalite, fersmite and microlite. Fissures generated in the Nb, Ta oxide minerals during deformation are filled with titanite, formed by reaction of the oxide minerals with metamorphic pore fluids. The titanite displays limited degrees of substitutions Na(Ta > Nb)(CaTi)−1, (Ta > Nb)4□Ti−4Si−1 and AI(OH, F)(TiO)−1, but an extensive (and occasionally the sole significant) substitution (Al > Fe3+)(Ta > Nb)Ti−2, responsible for widespread oscillatory zoning. This substitution reduces the proportion of the titanite componentsensu stricto, CaTiSiO4,O, to less than 50 mole % in many analyzed spots. The extreme composition corresponds to (Ca0.994Na0.011)(Ti0.436Sn0.007Al0.280Fe3+0.006Ta0.199Nb0.079)Si0.988O4(O0.974F0.026). However, so far this substitution fails to generate compositions that would define a new species.ZusammenfassungDie AI(Nb, Ta)Ti−2 Substitution im Titanit: Auftauchen einer neuen Mineralspecies? Die höchsten (Nb, Ta) Gehalte, die jemals für Titanit gefunden wurden, werden für den Maršíkov II Pegmatit in Nordmähren, Tschechei, berichtet. Der Intrusivgang ist Teil eines Amphibolit-faziell überprägten Pegmatitschwarms vom Beryll-Columbit Subtypus Der Pegmatit führt u.a. seltene tantalbetonte Rutile verwachsen mit titanbetontem Ixiolith, titanbetontem Columbit-Tantalit, Fersmit and Mikrolith. Deformationsbedingte Frakturen in den (Nb, Ta) Oxiden sind mit Titanit, als Folge der Reaktion der metamorphen Porenlösungen mit den Oxidmineralen, verkittet. Titanit zeigt begrenzte Substitutionen Na(Ta > Nb)(CaTi)−1,(Ta > Nb)4□Ti−4Si−1 and Al(OH, F)(TiO)−1, aber extensive (und gelegentlich einzig bedeutsame) Substitution (Al >> Fe3+)(Ta > Nb)Ti−2, die eine weitverbreitete, oszillierende Zonierung hervorruft. Diese Substitution verringert den Anteil der Titanit-Komponentesensu stricto, CaTiSiO,O, auf weniger als 50 Mol% in vielen Analysen. Die Extremzusammensetzung entspricht Ca0.994Na0.11) (T10.436Sn0.007Al0.280Fe3+0.006Ta0.199Nb0.079)Si0.988O4(O0.974F0.026). Das AusmaB dieser Substitution ist unzureichend, um eine neue Mineralspecies zu definieren.

Sejkoraite-(Y), a new member of the zippeite group containing trivalent cations from Jáchymov (St. Joachimsthal), Czech Republic: Description and crystal structure refinement

Abstract Sejkoraite-(Y), the triclinic (Y1.98Dy0.24)Σ2.22H+ 0.34[(UO2)8O88O7OH(SO4)4](OH)(H2O)26, is a new member of the zippeite group from the Červená vein, Jáchymov (Street Joachimsthal) ore district, Western Bohemia, Czech Republic. It grows on altered surface of relics of primary minerals: uraninite, chalcopyrite, and tennantite, and is associated with pseudojohannite, rabejacite, uranopilite, zippeite, and gypsum. Sejkoraite-(Y) forms crystalline aggregates consisting of yellow-orange to orange crystals, rarely up to 1 mm in diameter. The crystals have a strong vitreous luster and a pale yellow-to-yellow streak. The crystals are very brittle with perfect {100} cleavage and uneven fracture. The Mohs hardness is about 2. The mineral is not fluorescent either in short- or long-wavelength UV radiation. Sejkoraite-(Y) is yellow, with no visible pleochroism, biaxial negative with α′ = 1.62(2), β′ = 1.662(3), γ′ = 1.73(1), 2Vcalc = 79°. The empirical chemical formula (mean of 8 electron microprobe point analyses) was calculated on the basis of 12 (S + U) atoms: (Y1.49Dy0.17Gd0.11Er0.07Yb0.05Sm0.02)Σ1.90H+ 0.54 [(UO2)8.19O7OH(SO4)3.81](H2O)26.00. Sejkoraite-(Y) is triclinic, space group P1̄, a = 14.0743(6), b = 17.4174(7), c = 17.7062(8) Å, α = 75.933(4), β = 128.001(5), γ = 74.419(4)°, V = 2777.00(19) Å3, Z = 2, Dcalc = 4.04 g/cm3. The seven strongest reflections in the X-ray powder diffraction pattern are [dobs in Å (I) (hkl)]: 9.28 (100) (100), 4.64 (39) (200), 3.631 (6) (1̄42), 3.451 (13) (1̄44), 3.385 (10) (2̅4̅2), 3.292 (9) (044), 3.904(7) (300), 2.984 (10) (1̄4̅2). The crystal structure of sejkoraite-(Y) has been solved by the charge flipping method from single-crystal X-ray diffraction data and refined to Robs = 0.060 with GOFobs = 2.38, based on 6511 observed reflections. The crystal structure consists of uranyl sulfate sheets of zippeite anion topology, which alternate with an interlayer containing Y3+(H2O)n polyhedra and uncoordinated H2O groups. Two yttrium atoms are linked to the sheet directly via uranyl oxygen atom, and the remaining one is bonded by hydrogen bonds only. In the Raman and infrared spectrum of sejkoraite-(Y) there are dominating stretching vibrations of SO4 tetrahedra (-1200-1100 cm-1), UO22+ stretching vibrations (-900-800 cm-1), and O-H stretching (-3500-3200 cm-1) and H-O-H bending modes (-1640 cm-1). The new mineral is named to honor Jiří Sejkora, a Czech mineralogist of the National Museum in Prague.

Crystal chemistry and origin of grandidierite, ominelite, boralsilite, and werdingite from the Bory Granulite Massif, Czech Republic

Abstract A mineral assemblage involving grandidierite, ominelite, boralsilite, werdingite, dumortierite (locally Sb,Ti-rich), tourmaline, and corundum, along with the matrix minerals K-feldspar, quartz, and plagioclase, was found in a veinlet cutting leucocratic granulite at Horní Bory, Bory Granulite Massif, Moldanubian Zone of the Bohemian Massif. Zoned crystals of primary grandidierite to ominelite enclosed in quartz are locally overgrown by prismatic crystals of boralsilite and Fe-rich werdingite. Boralsilite also occurs as separate cross-shaped plumose aggregates with Fe-rich werdingite in quartz. Grandidierite is commonly rimmed by a narrow zone of secondary tourmaline or is partially replaced by the assemblage tourmaline + corundum ± hercynite. Grandidierite (XFe = 0.34-0.71) exhibits dominant FeMg-1 substitution and elevated contents of Li (120-1890 ppm). Boralsilite formula ranges from Al15.97B6.20Si1.80O37 to Al15.65B5.29Si2.71O37 and the formula of werdingite ranges from (Fe,Mg)1.44Al14.61B4.00Si3.80O37 to (Fe,Mg)1.22Al14.86B4.25Si3.55O37. Dumortierite and Sb,Ti-rich dumortierite occur as zoned crystals with zones poor in minor elements (≤0.12 apfu Fe+Mg) and zones enriched in Sb (≤0.46 apfu) and Ti (≤0.25 apfu). Secondary tourmaline (XFe = 0.44-0.75) of the schorlmagnesiofotite- foitite-olenite solid solution occurs as a replacement product of grandidierite, rarely boralsilite. Other accessory minerals in the veinlet include monazite-(Ce), ilmenite, rutile, ferberite, srilankite, löllingite, arsenopyrite, and apatite. Formation of the borosilicate-bearing veinlet post-dates the development of foliation in the host granulite and is related to the decompressional process. The assemblage most probably originated from a H2O-poor system at T ~ 750 °C and P ~ 6-8 kbar. Textural relations as well as geological position of the borosilicate veinlet suggest that it represents the earliest intrusion related to pegmatites in the Bory Granulite Massif. Younger granitic pegmatites in the area are characterized by high contents of B, Al, P, Fe, and minor concentrations of W, Ti, Zr, Sc, and Sb. All pegmatite types probably formed within a short time period of ~5 Ma.

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).

Rubidium- and cesium-dominant micas in granitic pegmatites

Abstract The mode of occurrence and chemical composition of five types of micas with Rb- or Cs-dominant populations of interlayer cations, collected from the Red Cross Lake rare-element pegmatites in north-central Manitoba, are described here. All five micas are candidates for new mineral species but crystal-structural data and Li contents could not be determined to date because of extremely small particle size, restricted to the margins of strongly zoned microcrystals. Based on electron-microprobe analyses, on Li contents estimated from Li/F (at.) = 1.0, and on bulk analysis of ferromagnesian micas for FeO and Fe2O3, the micas correspond to Rb- and Cs-dominant polylithionite (with representative interlayer populations of Rb0.82K0.12Cs0.07 and Cs0.74Rb0.12K0.08 apfu, respectively), Rb and Cs-dominant magnesian annite (Rb45K0.37Cs0.20 and Cs0.67Rb0.20K0.12 apfu, respectively), and Cs-dominant ferroan phlogopite (Cs0.92Rb0.04K0.02 apfu).