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Štěpite, U(AsO3OH)2·4H2O, from Jáchymov, Czech Republic: the first natural arsenate of tetravalent uranium
- J. Plášil, K. Fejfarová, J. Hloušek, R. Škoda, M. Novák, J. Sejkora, J. Čejka, M. Dušek, F. Veselovský, P. Ondruš, J. Majzlan, Z. Mrázek
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 1 / February 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 137-152
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Štěpite, tetragonal U(AsO3 OH)2(H2O)4 (IMA 2012-006), is the first natural arsenate of tetravalent uranium. It occurs in the Geschieber vein, Jáchymov ore district, Western Bohemia, Czech Republic, as emerald-green crystalline crusts on altered arsenic. Associated minerals include arsenolite, běhounekite, claudetite, gypsum, kaatialaite, the new mineral vysokýite (IMA 2012-067) and a partially characterized phase with the formula (H3O)+2(UO2)2(AsO4)2˙6H2O. Štěpite typically forms tabular crystals with prominent {001} and {010} faces, up to 0.6 mm in size. The crystals have a vitreous lustre and a grey to greenish grey streak. They are brittle with an uneven fracture and a very good cleavage on (001). Their Mohs hardness is about 2. Štěpite is not fluorescent in either short-wave or long-wave ultraviolet light. It is biaxial (–) with refractive indices (at 590 nm) of α = 1.636(2), β = 1.667(3), γ = 1.672(2) and 2Vobs < ~5°, anomalous greyish to pale yellow interference colours, and no pleochroism. The composition is as follows: 0.12Na2O, 50.19 UO2, 0.04SiO4, 0.09 P2O5, 0.93 As2O5, 1.95 SO3, 16.41 H2O; total 107.90 wt.%, yielding an empirical formula (based on 12 O a. p. f. u.) of (U1.01Na0.02)Σ1.03[(AsO3OH)1.82 (PO3OH)0.04(SO4)0.13(SiO4)0.01]Σ 2.00˙4H2O. Štěpite is tetragonal, crystallizing in space group I41/acd, with a = 10.9894(1), c = 32.9109(6) Å, V = 3974.5(1) Å3, Z = 16 and Dcalc = 3.90 g cm-3. The six strongest peaks in the X-ray powder-diffraction pattern [dobs in Å (I) (hkl)] are as follows: 8.190(100)(004), 7.008(43)(112), 5.475(18)(200), 4.111(16)(008), 3.395(20)(312,217), 2.1543(25)(419). The crystal structure of šteěpite has been solved from singlecrystal X-ray diffraction data by the charge-flipping method and refined to R1 = 0.0353 based on 1434 unique observed reflections, and to wR2 = 0.1488 for all 1523 unique reflections. The crystal structure of štšpite consists of sheets perpendicular to [001], made up of eight-coordinate uranium atoms and hydroxyarsenate 'tetrahedra'. The ligands surrounding the uranium atom consist of six oxygen atoms which belong to the hydroxyarsenate groups and two oxygen atoms which belong to interlayer H2 O molecules. Each UO8 polyhedron is connected to five other U polyhedra via six AsO3OH groups. Adjacent electroneutral sheets, of composition [U4+(AsO3OH)22-]0, are linked by hydrogen bonds involving H2 O molecules in the interlayers and OH groups in the sheets. The new mineral is named in honour of Josef Štěp (1863–1926), a Czech mining engineer and 'father' of the world's first radioactive spa at Jáchymov.
Švenekite, Ca[AsO2(OH)2]2, a new mineral from Jáchymov, Czech Republic
- P. Ondruš, R. Skála, J. Plášil, J. Sejkora, F. Veselovský, J. Čejka, A. Kallistová, J. Hloušek, K. Fejfarová, R. Škoda, M. Dušek, A. Gabašová, V. Machovič, L. Lapčák
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 6 / August 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 2711-2724
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Švenekite (IMA 99-007), Ca[AsO2(OH)2]2, is a rare supergene arsenate mineral occurring in the Geschieber vein, Jáchymov ore district, Western Bohemia, Czech Republic. It grows directly on the granite rocks and occurs isolated from other arsenate minerals otherwise common in Jáchymov. Švenekite usually forms clear transparent coatings composed of indistinct radiating to rosette-shaped aggregates up to 3 mm across. They are composed of thin lens- or bladed-shaped crystals, usually 100 – 150 μm long. Švenekite is transparent to translucent and has a white streak and a vitreous lustre; it does not fluoresce under ultraviolet light. Cleavage is very good on {010}. The Mohs hardness is ∼2. Švenekite is biaxial, non-pleochroic. The refractive indices are α' = 1.602(2), γ' = 1.658(2). The empirical formula of švenekite (based on As + P + S = 2 a.p.f.u., an average of 10 spot analyses) is (Ca1.00Mg0.01)Σ1.01[AsO2(OH)2]1.96[PO2(OH)2]0.03(SO4)0.01. The simplified formula is Ca[AsO2(OH)2]2 and requires CaO 17.42, As2O571.39, H2O 11.19, total 100.00 wt.%. Raman and infrared spectroscopy exhibit dominance of O – H vibrations and vibration modes of distorted tetrahedral AsO2(OH)2 units. Švenekite is triclinic, space group P, with a = 8.5606(5), b = 7.6926(6), c = 5.7206(4) Å, α = 92.605(6), β = 109.9002(6), γ = 109.9017(6)º, and V = 327.48(4) Å3, Z = 2, Dcalc = 3.26 g·cm–3. The a:b:c ratio is 0.7436:1:1.1082 (for single-crystal data). The six strongest diffraction peaks in the X-ray powder diffraction pattern are [d (Å)/I(%)/(hkl)]: 3.968(33)(20); 3.766(35)(2); 3.697(49)(101); 3.554(100)(020); 3.259(33)(20); 3.097(49)(11). The crystal structure of švenekite was refined from single-crystal X-ray diffraction data to R1 = 0.0250 based on 1309 unique observed, and to wR2 = 0.0588, for all 1588 unique reflections (with GOFall = 1.20). The structure of švenekite consists of sheets of corner-sharing CaO8 polyhedra and AsO2 OH2 groups, stacked parallel to (001). Adjacent sheets are linked by hydrogen bonds. The švenekite structure possesses very short symmetrical hydrogen bonds (with the D–H lengths ∼1.22 Å). The mineral is named to honour Jaroslav Švenek, the former curator of the mineralogical collection of the National Museum in Prague, Czech Republic.
The crystal chemistry of the uranyl carbonate mineral grimselite, (K, Na)3Na[(UO2)(CO3)3](H2O), from Jáchymov, Czech Republic
- J. Plášil, K. Fejfarová, R. Skála, R. Škoda, N. Meisser, J. Hlousek, I. Císařová, M. Dušek, F. Veselovský, J. Čejka, J. Sejkora, P. Ondruš
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- Journal:
- Mineralogical Magazine / Volume 76 / Issue 3 / June 2012
- Published online by Cambridge University Press:
- 05 July 2018, pp. 443-453
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Two crystals of the uranyl carbonate mineral grimselite, ideally K3Na[(UO2)(CO3)3](H2O), from Jáchymov in the Czech Republic were studied by single-crystal X-ray diffraction and electron-probe microanalysis. One crystal has considerably more Na than the ideal chemical composition due to substitution of Na into KO8 polyhedra; the composition of the other crystal is nearer to ideal, and similar to synthetic grimselite. The presence of Na atoms in KO8 polyhedra, which are located in channels in the crystal structure, reduces their volume, and as a result the unit-cell volume also decreases. Structure refinement shows that the formula for the sample with the anomalously high Na content is (K2.43Na0.57)Σ3.00Na[(UO2)(CO3)3](H2O). The unit-cell parameters, refined in space group P2c, are a = 9.2507(1), c = 8.1788(1) Å, V = 606.14(3) Å3 and Z = 2. The crystal structure was refined to R1 = 0.0082 and wR1 = 0.0185 with a GOF = 1.33, based on 626 observed diffraction peaks [Iobs>3σ(I)].
Hloušekite, (Ni,Co)Cu4(AsO4)2(AsO3OH)2(H2O)9, a new member of the lindackerite supergroup from Jáchymov, Czech Republic
- J. Plášil, J. Sejkora, R. Škoda, M. Novák, A. V. Kasatkin, P. Škácha, F. Veselovský, K. Fejfarová, P. Ondruš
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- Journal:
- Mineralogical Magazine / Volume 78 / Issue 5 / October 2014
- Published online by Cambridge University Press:
- 05 July 2018, pp. 1341-1353
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Hloušekite, (Ni,Co)Cu4(AsO4)2(AsO3OH)2(H2O)9, is a new supergene arsenate mineral from the Geister vein (Rovnost mine), Jáchymov (St Joachimsthal), Western Bohemia, Czech Republic. It was found along with veselovský ite, pradetite, lavendulan, arsenolite, babánekite and gypsum on the surface of strongly altered ore fragments containing dominant tennantite and chalcopyrite. Hloušekite forms thin, lath-like crystals, locally elongated reaching up to 3 mm across. It is transparent, has a pale green colour with vitreous lustre, has a greyish-white streak and it is very brittle with an uneven fracture. It does not fluoresce under shortwave or longwave ultraviolet radiation. Cleavage on {010} is perfect; the Mohs hardness is 2–3. The calculated density is 3.295 g cm–3. Hloušekite is optically biaxial with α’ = 1.653(2) and γ’ = 1.73. The estimated optical orientation is γ’ vs. elongation (c) = 14(1)°. In larger grains it is weakly to moderately pleochroic (α = colourless, γ = pale green to green). Hloušekite is triclinic, space group P, a = 6.4010(6), b = 8.0041(6), c = 10.3969(14) Å , α = 85.824(8), β = 79.873(9), γ = 84.655(7)° and V = 521.23(10) Å3, with Z = 1, a:b:c = 0.800:1:1.299. The eight strongest lines in the powder X-ray diffraction (XRD) pattern [d in Å (I)(hkl)] are 10.211(100)(001), 7.974(9)(010), 3.984(6)(020), 3.656(5)(12), 3.631(5)(01), 3.241(5)(022), 3.145(5)(200) and 3.006(5)(210). Chemical analysis by electron microprobe yielded MgO0.20, FeO0.10, NiO 5.79, CoO1.80, CuO29.53, ZnO 0.66, Al2O3 0.14, P2O5 0.11, As2O5 45.01, H2O 17.71 (calc.), for a total of 101.05 wt.%. The resulting empirical formula, calculated by stoichiometry (9H2O + 2OH), obtained from the crystal structure, is (Ni0.79Co0.25)Σ1.04(Cu3.78Zn0.08Mg0.05Al0.03Fe0.01)Σ3.95 (AsO4 )1.98(PO4 )0.02(AsO3OH)2.00(H2O)9.00 . The ideal endmember formula , NiCu4(AsO4)2(AsO3OH)2(H2O)9.00, requires NiO7.23, CuO30.81, As2O5 44.51, H2O17.45, total 100.00 wt.%. The crystal structure of hloušekite was solved by charge flipping from single-crystal XRD data and refined to R1 = 0.0599 for 1441 reflections with [Iobs > 3σ(I)]. Hloušekite is a new member of the lindackerite group (also including lindackerite, pradetite and veselovský ite) of the lindackerite supergroup. The ondrušite group of the lindackerite supergroup includes ondrušite, chudobaite, geigerite and klajite. The establishment of these two groups reflects the difference between the crystal structures of their members, mainly in the coordination environment of the Me cations.