Volume 81 - December 2017
Research Article
Crystal-chemical aspects of the roméite group, A2Sb2O6Y, of the pyrochlore supergroup
- Ferdinando Bosi, Andrew G. Christy, Ulf Hålenius
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- 26 January 2018, pp. 1287-1302
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Four specimens of the roméite-group minerals oxyplumboroméite and fluorcalcioroméite from the Långban Mn-Fe deposit in Central Sweden were structurally and chemically characterized by single-crystal X-ray diffraction, electron microprobe analysis and infrared spectroscopy. The data obtained and those on additional roméite samples from literature show that the main structural variations within the roméite group are related to variations in the content of Pb2+, which is incorporated into the roméite structure via the substitution Pb2+→A2+ where A2+ = Ca, Mn and Sr. Additionally, the cation occupancy at the six-fold coordinated B site, which is associated with the heterovalent substitution BFe3+ + Y☐→BSb5++YO2-, can strongly affect structural parameters.
Chemical formulae of the roméite minerals group are discussed. According to crystal-chemical information, the species associated with the name ‘kenoplumboroméite’, hydroxycalcioroméite and fluorcalcioroméite most closely approximate end-member compositions Pb2(SbFe3+)O6☐, Ca2(Sb5+Ti) O6(OH) and (CaNa)Sb2O6F, respectively. However, in accord with pyrochlore nomenclature rules, their names correspond to multiple end-members and are best described by the general formulae: (Pb,#)2(Sb,#)2O6☐, (Ca,#)2(Sb,#)2O6(OH) and (Ca,#)Sb2(O,#)6F, where ‘#’ indicates an unspecified charge-balancing chemical substituent, including vacancies.
Lucchesiite, CaFe2+3Al6(Si6O18)(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup
- Ferdinando Bosi, Henrik Skogby, Marco E. Ciriotti, Petr Gadas, Milan Novák, Jan Cempírek, Dalibor Všianský, Jan Filip
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- 02 January 2018, pp. 1-14
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Lucchesiite, CaFe32+Al6(Si6O18)(BO3)3(OH)3O, is a new mineral of the tourmaline supergroup. It occurs in the Ratnapura District, Sri Lanka (6°35'N, 80°35'E), most probably from pegmatites and in Mirošov near Strážek, western Moravia, Czech Republic, (49°27'49.38"N, 16°9'54.34"E) in anatectic pegmatite contaminated by host calc-silicate rock. Crystals are black with a vitreous lustre, conchoidal fracture and grey streak. Lucchesiite has a Mohs hardnessof ∼7 and a calculated density of 3.209 g/cm3 (Sri Lanka) to 3.243 g/cm3 (Czech Republic). In plane-polarized light, lucchesiite is pleochroic (O = very dark brown and E = light brown) and uniaxial (–). Lucchesiite is rhombohedral, space group R3m, a ≈ 16.00 Å, c ≈ 7.21 Å, V ≈ 1599.9 Å3, Z = 3. The crystal structure of lucchesiite was refined to R1 ≈ 1.5% using ∼2000 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis for the Sri Lanka (holotype) and Czech Republic (cotype) samples resulted in the empirical formulae, respectively: X(Ca0.69Na0.30K0.02)∑1.01Y(Fe1.442+Mg0.72Al0.48Ti0.334+V0.023+Mn0.013+Zn0.01)∑3.00Z(Al4.74Mg1.01Fe0.253+)∑6.00[T(Si5.85Al0.15)∑6.00O18](BO3)3V(OH)3W[O0.69F0.24(OH)0.07]∑1.00and X(Ca0.49Na0.45□0.05 K0.01)∑1.00Y(Fe1.142+Fe0.953+Mg0.42Al0.37Mn0.03Ti0.084+Zn0.01)∑3.00Z(Al5.11Fe0.383+Mg0.52)∑6.00[T(Si5.88Al0.12)∑6.00O18](BO3)3V[(OH)2.66O0.34]∑3.00W(O0.94F0.06)∑1.00.
Lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. The closest end-member composition of a valid tourmaline species is that of feruvite, to which lucchesiite is ideally related by the heterovalent coupled substitution ZAl3++O1O2– ↔ ZMg2+ + O1(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2015-043).
Leószilárdite, the first Na,Mg-containing uranyl carbonate from the Markey Mine, San Juan County, Utah, USA
- Travis A. Olds, Luke R. Sadergaski, Jakub Plášil, Anthony R. Kampf, Peter C. Burns, Ian M. Steele, Joe Marty, Shawn M. Carlson, Owen P. Mills
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- 02 January 2018, pp. 1039-1050
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Leószilárdite (IMA2015-128), Na6Mg(UO2)2(CO3)6·6H2O, was found in the Markey Mine, Red Canyon, White Canyon District, San Juan County, Utah, USA, in areas with abundant andersonite, natrozippeite, gypsum, anhydrite, and probable hydromagnesite along with other secondary uranium minerals bayleyite, čejkaite and johannite. The new mineral occurs as aggregates of pale yellow bladed crystals flattened on ﹛001﹜ and elongated along [010], individually reaching up to 0.2 mmlong. More commonly it occurs as pale yellow pearlescent masses to 2 mm consisting of very small plates. Leószilárdite fluoresces green under both longwave and shortwave ultraviolet light, and is translucent with a white streak, hardness of 2 (Mohs), and brittle tenacity with uneven fracture. The new mineral is readily soluble in room temperature H2O. Crystals have perfect cleavage along ﹛001﹜, and exhibit the forms ﹛110﹜,﹛001﹜,﹛100﹜,﹛101﹜ and ﹛101﹜. Optically, leószilárdite is biaxial (-), α= 1.504(1), β= 1.597(1), γ= 1.628(1) (white light); 2V (meas.) = 57(1)°, 2V (calc.) = 57.1°; dispersion r > v, slight. Pleochroism: X= colourless, Y and Z= light yellow; X<Y ≈ Z The average of six wavelength dispersive spectroscopic analyses provided Na2O 14.54, MgO 3.05, UO3 47.95, CO2 22.13, H2O 9.51, total 97.18 wt.%. The empirical formula is Na5.60Mg0.90U2O28C6H12.60, based on 28 O apfu. Leószilárdite is monoclinic, C2/m, a = 11.6093(21), b = 6.7843(13), c = 15.1058(28) Å, β = 91.378(3)°, V= 1189.4(4) Å3 and Z = 2. The crystal structure (R1 = 0.0387 for 1394 reflections with Iobs > 4σI), consists of uranyl tricarbonate anion clusters [(UO2)(CO3)3]4- held together in part by irregular chains of NaO5(H2O) polyhedra sub parallel to [010]. Individual uranyl tricarbonate clusters are also linked together by three-octahedron units consisting of two Na-centred octahedra that share the opposite faces of a Mg-centred octahedron at the centre (Na–Mg–Na), and have the composition Na2MgO12(H2O)4. The name of the new mineral honours the Hungarian-American physicist, inventor and biologist Dr. Leó Szilárd (1898–1964).
The REE- and HFSE-bearing phases in the Itatiaia alkaline complex (Brazil) and geochemical evolution of feldspar-rich felsic melts
- Leone Melluso, Vincenza Guarino, Michele Lustrino, Vincenzo Morra, Roberto de' Gennaro
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- 02 January 2018, pp. 217-250
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The Late Cretaceous Itatiaia complex is made up of nepheline syenite grading to peralkaline varieties, quartz syenite and granite, emplaced in the metamorphic rocks of the Serra do Mar, SE Brazil. The nepheline syenites are characterized by assemblages with alkali feldspar, nepheline, Fe-Ti oxides, clinopyroxene, amphibole, apatite and titanite, while the peralkaline nepheline syenites have F-disilicates (rinkite, wöhlerite, hiortdahlite, låvenite), britholite and pyrophanite as the accessory phases. The silica-oversaturated rocks have alkali feldspar, plagioclase, quartz, amphibole, clinopyroxene and Fe-Ti oxides; the chevkinite-group minerals are the featured accessory phases and are found with allanite, fluorapatite, fluorite, zircon, thorite, yttrialite, zirconolite, pyrochlore and yttrocolumbite. The major- and trace-element composition of the Itatiaia rocks have variations linked to the amount of accessory phases, have smooth, enriched chondritenormalized rare-earth element (REE) distribution patterns in the least-evolved nepheline syenites and convex patterns in the most-evolved nepheline syenites. The REE distribution patterns of the quartz syenites and granites show a typical pattern caused by fractional crystallization of feldspar and amphibole, in an environment characterized by relatively high oxygen fugacity (>NiNiO buffer) and high concentrations of H2O and F, supporting the crystallization of hydrous phases, fluorite and F-disilicates. The removal of small amounts of titanite in the transition from the least-evolved to the most-evolved nepheline syenites stems from petrogenetic models involving REE, and is shown to be a common feature of the magmatic evolution of many other syenitic/ trachytic/ phonolitic complexes of the Serra do Mar and elsewhere.
Oxynatromicrolite, (Na,Ca,U)2Ta2O6(O,F), a new member of the pyrochlore supergroup from Guanpo, Henan Province, China
- Fan Guang, Ge Xiangkun, Li Guowu, Yu Apeng, Shen Ganfu
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- 02 January 2018, pp. 743-751
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A new mineral species of the pyrochlore supergroup, oxynatromicrolite (IMA2013-063), (Na,Ca,U)2Ta2O6O, was found in the No. 309 rare-metal granitic pegmatite vein, Guanpo, Lushi county, Henan Province, China, which is characterized by tantalum at theB site and oxygen at the Y site and is Na dominant at the A site. The mineral occurs as strongly metamict, and mostly euhedral octahedral crystals up to 0.05–0.20 mm across. The measured density of an unheated sample is 6.580(4) g cm–3, and the calculatedone is 6.506 g cm–3. Optically, the mineral is isotropic, with an index of refraction 1.999(5) and a reflectance of 11.88% (470 nm). When heated to 1000°C for 4 hours in N2, the mineral recrystallizes in the cubic system, with space group Fd3mand with unit-cell parameters similar those of other pyrochlore supergroup species: a = 10.420(6) Å, V = 1131.4(2) Å3. Electron microprobe analyses revealed the following composition of the mineral (in wt.%): Na2O 5.41, CaO 4.56, UO214.60, La2O3 0.16, Ce2O3 0.11, Nd2O3 0.13, PbO 0.62, Ta2O5 61.52, Nb2O5 8.21, Sb2O5 0.23, TiO2 0.05, SiO2 0.56, SnO2 0.29, F1.04, H2O 1.50 (calculated to correspond to 0.47 H2O pfu), F≡O –0.44, sum = 98.53%, which corresponds to the empirical formula (Na0.99Ca0.46U0.31Pb0.02La0.01H2O0.21)∑2.00(Ta1.58Nb0.35Si0.05Sn0.01Sb0.01)∑2.00O6 (O0.43F0.31H2O0.26)∑1.00, represented by the simplified formula (Na,Ca,U)2(Ta,Nb)2O6(O,F).Oxynatromicrolite crystallized during the late-stage of formation for the No. 309 pegmatite dyke and is associated with quartz, albite, potassium feldspar, muscovite, kaolinite, tantalite-Mn, stibiotantalite, pollucite, spodumene, montebrasite, Hf-rich zircon, a red tourmaline, polylithionite,trilithionite, luanshiweiite-2M1 (IMA2011-102) and a hydrated derivative of oxynatromicrolite.
Nomenclature of the perovskite supergroup: A hierarchical system of classification based on crystal structure and composition
- Roger H. Mitchell, Mark D. Welch, Anton R. Chakhmouradian
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- 02 January 2018, pp. 411-461
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On the basis of extensive studies of synthetic perovskite-structured compounds it is possible to derive a hierarchy of hettotype structures which are derivatives of the arisotypic cubic perovskite structure (ABX3), exemplified by SrTiO3 (tausonite) or KMgF3 (parascandolaite) by: (1) tilting and distortion of the BX6 octahedra; (2) ordering of A- and B-site cations; (3) formation of A-, B- or X-site vacancies. This hierarchical scheme can be applied to some naturally-occurring oxides, fluorides,hydroxides, chlorides, arsenides, intermetallic compounds and silicates which adopt such derivative crystal structures. Application of this hierarchical scheme to naturally-occurring minerals results in the recognition of a perovskite supergroup which is divided into stoichiometric and non-stoichiometricperovskite groups, with both groups further divided into single ABX3 or double A2BB'X6 perovskites. Subgroups, and potential subgroups, of stoichiometric perovskites include: (1) silicate single perovskites of the bridgmanite subgroup;(2) oxide single perovskites of the perovskite subgroup (tausonite, perovskite, loparite, lueshite, isolueshite, lakargiite, megawite); (3) oxide single perovskites of the macedonite subgroup which exhibit second order Jahn-Teller distortions (macedonite, barioperovskite); (4) fluoride singleperovskites of the neighborite subgroup (neighborite, parascandolaite); (5) chloride single perovskites of the chlorocalcite subgroup; (6) B-site cation ordered double fluoride perovskites of the cryolite subgroup (cryolite, elpasolite, simmonsite); (7) B-site cation orderedoxide double perovskites of the vapnikite subgroup [vapnikite, (?) latrappite]. Non-stoichiometric perovskites include: (1) A-site vacant double hydroxides, or hydroxide perovskites, belonging to the söhngeite, schoenfliesite and stottite subgroups; (2) Anion-deficient perovskitesof the brownmillerite subgroup (srebrodolskite, shulamitite); (3) A-site vacant quadruple perovskites (skutterudite subgroup); (4) B-site vacant single perovskites of the oskarssonite subgroup [oskarssonite]; (5) B-site vacant inverse single perovskites of the coheniteand auricupride subgroups; (6) B-site vacant double perovskites of the diaboleite subgroup; (7) anion-deficient partly-inverse B-site quadruple perovskites of the hematophanite subgroup.
Klaprothite, péligotite and ottohahnite, three new minerals with bidentate UO7–SO4 linkages from the Blue Lizard mine, San Juan County, Utah, USA
- Anthony R. Kampf, Jakub Plášil, Anatoly V. Kasatkin, Joe Marty, Jiří Čejka
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- 02 January 2018, pp. 753-779
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The new minerals klaprothite (IMA2015-087), Na6(UO2)(SO4)4(H2O)4, péligotite (IMA2015-088), Na6(UO2)(SO4)4(H2O)4 and ottohahnite (IMA2015-098),Na6(UO2)2(SO4)5(H2O)7·1.5H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary phases. All three minerals occur as yellowish-green to greenish-yellow crystals, are brittle with irregular fracture, have Mohs hardness of ∼2½ and exhibit bright bluish-green fluorescence, and all are easily soluble in room temperature H2O. Only klaprothite exhibits cleavage; perfect on {100} and {001}. Quantitative energydispersive spectroscopy analyses yielded the empirical formulas Na6.01(U1.03O2)(S0.993O4)4(H2O)4, Na5.82(U1.02O2)(S1.003O4)4(H2O)4 and Na5.88(U0.99O2)2(S1.008O4)5(H2O)8.5 for klaprothite, péligotite and ottohahnite, respectively. Their Raman spectra exhibit similar features. Klaprothite is monoclinic, P21/c, a = 9.8271(4), b = 9.7452(3), c = 20.8725(15) Å, β = 98.743(7)°, V = 1975.66(17)Å3 and Z = 4. Péligotite is triclinic, P1̄, a = 9.81511(18), b = 9.9575(2), c = 10.6289(8) Å, α = 88.680(6)°, β = 73.990(5)°, γ = 89.205(6)°, V = 998.22(8) Å3 and Z =2. Ottohahnite is triclinic, P1̄, a = 9.97562(19), b = 11.6741(2), c = 14.2903(10) Å, α = 113.518(8)°, β = 104.282(7)°, γ = 91.400(6)°, V = 1464.59(14) Å3 and Z = 2. The structures of klaprothite(R1 = 2.22%) and péligotite (R1 = 2.28%) both contain [(UO2)(SO4)4]6– clusters in which one SO4 group has a bidentate linkage with the UO7 polyhedron; Na–O polyhedra linkclusters into thick heteropolyhedral layers and link layers into frameworks; the structures differ in the configuration of Na–O polyhedra that link the layers. The structure of ottohahnite (R1 = 2.65%) contains [(UO2)4(SO4)10]12–clusters in which each UO7 polyhedron has a bidentate linkage with one SO4 group; Na–O polyhedra link clusters into a thin heteropolyhedral slice and also link the slices into a framework. The minerals are named for Martin Heinrich Klaproth (1743–1817), Eugène-MelchiorPéligot (1811–1890) and Otto Hahn (1879–1968).
Crystal chemistry of zinc incorporation in strunzite-group minerals containing zeolitic water
- I. E. Grey, E. Keck, C. M. MacRae, A. M. Glenn, A. R. Kampf, B. P. Nash, S. J. Mills
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- 02 January 2018, pp. 1051-1062
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A comparative study is presented of the chemistry and crystallography of zinc-bearing strunzites from Hagendorf Süd, Bavaria, Germany and the Sitio do Castelo mine, Folgosinho, Portugal. Electron microprobe analyses of samples from the two localities show quite different cation substitutions. The Hagendorf Süd mineral is a Zn-bearing ferristrunzite, with compositional zoning due to Zn2+ replacing predominantly Fe3+ as well as minor Mn2+, whereas the Portugese mineral is a Zn-bearing strunzite, in which Zn2+ replaces Mn2+, with minor replacement of Fe3+ by Mn3+. Zincostrunzite, with dominant Zn in the interlayer octahedrally coordinated site, is a new strunzite-group mineral that has been characterized at both locations. Analysis of single-crystal synchrotron data for zinc-bearing ferristrunzite and zincostrunzite crystals from Hagendorf Süd show that the structures of both minerals contain zeolitic water in the interlayer region. The formula for strunzite-group minerals containing the zeolitic water is MFe23+(PO4)2(OH)2·6.5H2O, M=Fe, Mn, Zn. This formulation agrees with that found for zincostrunzite from the Sitio do Castelo mine, but differs from that reported previously for strunzite, MFe2+(PO4)2(OH)2·6H2O, which has no interlayer water. Interestingly, the zincostrunzites from the two localities differ in the location of the interlayer water molecule, with a corresponding difference in the H bonding.
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- 02 January 2018, p. 461
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Research Article
Polloneite, a new complex Pb(-Ag)-As-Sb sulfosalt from the Pollone mine, Apuan Alps, Tuscany, Italy
- Dan Topa, Frank N. Keutsch, Emil Makovicky, Uwe Kolitsch, Werner Paar
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- 26 January 2018, pp. 1303-1322
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Polloneite, ideally AgPb46As26Sb23S120, is a new N = 4 member of the sartorite homologous series. It occurs in a matrix of baryte from the Pizzone level of the Pollone baryte-pyrite-(Pb-Zn-Ag) deposit at Valdicastello Carducci, near Pietrasanta, in the Apuan Alps, Tuscany, Italy, as anhedral grains up to 0.5 mm across. The mineral is opaque, greyish black with a metallic lustre. In reflected light polloneite is white, bireflectance is moderate. Internal reflections are absent. Under crossed polars, anisotropism is moderate with rotation tints in brown-violet and deep grey. The reflectance data (%, air) are: 30.2, 42.4 at 470 nm, 28.8, 41.0 at 546 nm, 27.9, 39.8 at 589 nm and 26.0, 37.4 at 650 nm. Mohs hardness is 3–3½, microhardness VHN50 exhibits a mean value of 200 kg mm-2. The average results of 15 electronmicroprobe analyses of three grains are Ag 0.71(5), Pb 52.05(21), As 10.61(22), Sb 15.40(12), S 21.16(8), total 99.92(15) wt.%, corresponding to Ag1.20Pb45.76As25.79Sb23.04S120.21 (on the basis of Me + S = 216 apfu). The simplified formula AgPb46As26Sb23S120 is in accordance with the results of a crystal structure determination. The calculated density is 5.77 g cm–3. Polloneite is monoclinic, space group P21, a = 8.413(2), b = 25.901(5), c = 23.818(5) Å, β = 90.01(3)°, V = 5189.8(18)Å3, Z = 1. The strongest eight lines in the calculated powder-diffraction pattern [d in Å(I)hkl] are 3.795(100)(026), 3.414(60)(233), 3.238(69)(080), 3.020(97)(253), 2.922(82)(066), 2.738(73)(236), 2.375(79)(290) and 2.103(64)(400). Polloneite is a new N = 4 member of the sartorite homologous series with substantial Sb and small, but important, Ag content. It is a three-fold superstructure with a tripled unit-cell parameter, 7.9 Å, of sartorite homologues. In the As-Sb rich slabs, several types of crankshaft chains and isolated (As,Sb)–S polyhedra occur. A sequence of three different, tightly bonded double-layer fragments (broad ribbons) contains two asymmetric fragments with long crankshaft chains whereas the third fragment type, with Ag, contains small mirror-symmetrical metalloid groups and no crankshaft chains. This configuration can potentially cause order-disorder phenomena in the structure. The threefold superstructure and the mixed As-Sb character distinguish polloneite from veenite and from dufrénoysite, respectively.
Structure refinement and crystal chemistry of tokkoite and tinaksite from the Murun massif (Russia)
- M. Lacalamita, E. Mesto, E. Kaneva, F. Scordari, G. Pedrazzi, N. Vladykin, E. Schingaro
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- 02 January 2018, pp. 251-272
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The structures of tokkoite, K2Ca4[Si7O18OH](OH,F) and tinaksite, K2Ca2NaTi[Si7O18OH]O from the Murun massif (Russia) were refined from single-crystal X-ray diffraction data in the triclinic space group P1̄. Average crystallographic data are a ≈ 10.423, b ≈ 12.477, c ≈ 7.112 Å, α ≈ 89.92°, β ≈ 99.68°, γ ≈ 92.97°, V ≈ 910.5 Å3 for tokkoite; a ≈ 10.373, b ≈ 12.176, c ≈ 7.057 Å, α ≈ 90.82°, β ≈ 99.22°, γ ≈ 92.80°, V ≈ 878.5 Å3 for tinaksite. The substantial similarities between the geometrical parameters of the tokkoite and tinaksite structures led us to conclude that the two minerals are isostructural. However, major differences of tokkoite with respect to tinaksite are larger lattice constants, especially concerning the b parameter, longer <M–O> distances, especially <M1–O>; larger values of the M1–M3 and O20–O2 bond lengths, and a stronger distortion of the M1 polyhedron. Mössbauer analysis showed that significant trivalent iron is present, VIFe3+ 40.0(7)% in tokkoite and 12.8(3)% in tinaksite. It is confirmed that 2Ca(M1+M2)2+ + (F,OH)(O20)–↔ Ti(M1)4+ + Na(M2)+ + O(O20)– is the exchange reaction that describes the relation between tokkoite and tinaksite. In addition, this exchange reaction causes local stress involving mainly the M1 site and its interaction with the M2 and M3 sites.
Lithium and trace-element concentrations in trioctahedral micas from granites of different geochemical types measured via laser ablation ICP-MS
- Karel Breiter, Michaela Vaňková, Michaela Vašinová Galiová, Zuzana Korbelová, Viktor Kanický
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- 02 January 2018, pp. 15-33
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The compositions of trioctahedral micas from 51 samples of granitoids with different geochemical affiliations and grades of differentiation from the Bohemian Massif, Central Europe, were analysed using electron microprobe (major elements) and laser ablation inductively coupled plasma mass spectrometry (Li, Sc, Ga, Ge, Nb, In, Sn, Cs, Ta, W, Tl). The micas form a continuous evolutionary series from phlogopite to zinnwaldite. The phlogopites and biotites from the I-type rocks are characterized by 5.5–5.7 Si, 2.4–2.6 Al, <0.1 Li atoms per formula unit [apfu] and Mg/(Mg + Fe) = 0.4–0.8. The biotites from the S-type granites usually contain 5.3–5.7 Si, 3.2–3.6 Al, 0.1–0.3 Li apfu and Mg/(Mg + Fe) = 0.15–0.4. The annites and zinnwaldites from the rare-metal granites contain 5.7–6.8 Si, 3.2–3.8 Al, 0.6–2.6 Li apfu and Mg/(Mg + Fe) < 0.1. The concentrations of F, Rb, Cs and Tl increase from the phlogopites and biotites to zinnwaldites: F 0.1 → 8 wt.%, Rb2O 0.05 → 1.7 wt.%, Tl 2 → 50 ppm and Cs 40 → 2000 ppm. The concentrations of Sn, Nb, Ta and W in phlogopites and biotites from the I- and S-type granitoids generally correlate with those of the parent rocks and reach values of (in ppm) 20–100 Sn, 20–250 Nb, 1–20 Ta and <5 W. The highest concentrations were found in the Li-annites in the relatively early facies of rare-metal granites (in ppm): 250–600 Sn, 400–600 Nb, 60–120 Ta and 50– 120 W. The zinnwaldites in the late rare-metal granites facies are impoverished in these elements, which is explained by contemporaneous crystallization of cassiterite and columbite. Lithium enters the crystal lattice of trioctahedral micas via the exchange vector Li3□Si3Fe–6Al–1 up to concentrations of ∼2.5 wt.% Li2O (1.5 apfu Li). At higher Li concentrations, Li is incorporated through the exchange vector Li3Si1□–1 Fe–2Al–1.
Bohseite, ideally Ca4Be4Si9O24(OH4, from the Piława Górna quarry, the Góry Sowie Block, SW Poland
- E. Szełęg, B. Zuzens, F. C. Hawthorne, A. Pieczka, A. Szuszkiewicz, K. Turniak, K. Nejbert, S. S. Ilnicki, H. Friis, E. Makovicky, M. T. Weller, M.-H. Lemée-Cailleau
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- 02 January 2018, pp. 35-46
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Bohseite is an orthorhombic calcium beryllium aluminosilicate with variable Al content and an endmember formula Ca4Be4Si9O24(OH4), that was discovered in the Piława Górna quarry in the eastern part of the Góry Sowie Block, ∼50 km southwest of Wrocław, SW Poland. It occurs in a zoned anatectic pegmatite dyke in close association with microcline, Cs-rich beryl, phenakite, helvite, 'lepidolite', probably bertrandite and unidentified Be-containing mica as alteration products after a primary Be mineral, probably beryl. Bohseite forms fan-like or parallel aggregates (up to 0.7 cm) of white, platy crystals (up to 2 mm long) with characteristic striations. It is white with a white streak, is translucent and has a vitreous lustre; it does not fluoresce under ultraviolet light. The cleavage is perfect on {001} and fair on {010}, and neither parting nor twinning was observed. Bohseite is brittle with a splintery fracture and Mohs hardness is 5–6. The calculated density is 2.719 g cm–3. The indices of refraction are α= 1.579, β = 1.580,γ = 1.597, all ±0.002; 2Vobs = 24(3)°, 2Vcalc = 27°; the optic orientation is as follows: X ^ a = 16.1°, Y ^ b = 16.1°, Z // c Bohseite shows orthorhombic diffraction symmetry, space group Cmcm, a = 23.204(6), b = 4.9442(9), c = 19.418(6) Å, V = 2227.7(4) Å3, Z = 4. The crystal structure was refined to an R1 value of 2.17% based on single-crystal data, and the chemical composition was determined by electron-microprobe analysis. Bohseite is isostructural with bavenite. Bohseite was originally approved with an end-member composition of Ca4Be3AlSi9O25(OH)3, but subsequent discovery of compositions with Be > 3.0 apfu led to redefinition of its end-member composition, holotype sample and locality, as reported here. There is extensive solid solution in bavenite–bohseite according to the scheme O(2)OH– + T(4)Si4+ + T(3)Be2+ ↔ O(2)O2– + T(4)Al3++ T(3)Si4+, and a general formula for the bavenite–bohseite minerals may be written as Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2–4 apfu: Ca4Be2Si9Al2O26(OH)2 (bavenite) to Ca4Be4Si9O24(OH)4 (bohseite).
Shumwayite, [(UO2)(SO4)(H2O)2]2·H2O, a new uranyl sulfate mineral from Red Canyon, San Juan County, Utah, USA
- Anthony R. Kampf, Jakub Plášil, Anatoly V. Kasatkin, Joe Marty, Jiří Čejka, Ladislav Lapčák
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- 02 January 2018, pp. 273-285
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The new mineral shumwayite (IMA2015-058), [(UO2)(SO4)(H2O)2]2·H2O, was found in the Green Lizard and Giveaway-Simplot mines, White Canyon district, San Juan County, Utah, USA, where it occurs as a secondary alteration phase. At the Green Lizard mine, it is found in association with calcite, gypsum, plášilite, pyrite, rozenite and sulfur; at the Giveaway-Simplot mine, shumwayite is associated with rhomboclase and römerite. The mineral occurs as pale greenish-yellow monoclinic prisms, elongated on [100], up to ∼0.3 mm long and commonly in subparallel to random intergrowths. The mineral is transparent with a vitreous lustre and has a white streak. It fluoresces bright greenish white under both longwave and shortwave ultraviolet radiation. The Mohs hardness is ∼2. Crystals are brittle with perfect {011} cleavage and irregular fracture. The mineral is slightly deliquescent and is easily soluble in room temperature H2O. The calculated density is 3.844 g cm–3. Optically, shumwayite is biaxial (+/–), with α = 1.581(1), β= 1.588(1), γ = 1.595(1) (measured in white light). The measured 2Vx based on extinction data collected on a spindle stage is 89.8(8)°; the calculated 2Vx is 89.6°. Dispersion is strong, but the sense is not defined because the optic sign is ambiguous. No pleochroism was observed. The optical orientation is X = b, Y = c, Z = a. Energy-dispersive spectrometer analyses (with H2O based on the crystal structure) yielded the empirical formula U2.01S1.99O12.00·5H2O.Shumwayite is monoclinic, P21/c, a = 6.74747(15), b = 12.5026(3), c = 16.9032(12) Å, β = 90.919(6)°, V = 1425.79(11) Å3 and Z = 4. The crystal structure (R1 = 1.88% for 2936 F > 4σF) contains UO7 pentagonal bipyramids and SO4 tetrahedra that link by corner-sharing to form [(UO2)(SO4)(H2O)2] chains along [100]. The chains and isolated H2O groups between them are linked together only by hydrogen bonds. The mineral is named in honour of the Shumway family, whose members account for the discovery and mining of hundreds of uranium deposits on the Colorado Plateau, including the Green Lizard mine.
Chemical and textural interpretation of late-stage coffinite and brannerite from the Olympic Dam IOCG-Ag-U deposit
- Edeltraud Macmillan, Nigel J. Cook, Kathy Ehrig, Allan Pring
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- 26 January 2018, pp. 1323-1366
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The Olympic Dam iron-oxide copper-gold-silver-uranium deposit, South Australia, contains three dominant U minerals: uraninite; coffinite; and brannerite. Microanalytical and petrographic observations provide evidence for an interpretation in which brannerite and coffinite essentially represent the products of U mineralizing events after initial deposit formation at 1.6 Ga. Marked compositional and textural differences between the various types of brannerite and coffinite highlight the role of multiple stages of U dissolution and reprecipitation.
On the basis of petrography (size, habit, textures and mineral associations) and compositional variation, brannerites are divided into four distinct groups (brannerite-A, -B, -C and -D), and coffinite into three groups (coffinite-A, -B and -C). Brannerite-A ranges in composition from what is effectively uraniferous rutile to stoichiometric brannerite, and has elevated (Mg +Mn + Na + K) and (Fe + Al) compared to other brannerite types. It displays the most diverse range of morphologies, including complex irregular-shaped aggregates, replacement bands, and discrete elongate seams. The internal structure of brannerite-A consists of randomly-oriented hair-like needles and blades. Brannerite-B (>5 μm in size) is generally prismatic and typically associated with baryte and REY minerals (REE+Y= REY). Brannerite-C and -D are both associated with Cu-(Fe)-sulfides and are typically composed of irregular masses and blebs (10–50 μm in size) with a more uniform or massive internal structure. Brannerite-D is distinct from -C and always contains inclusions of galena. Brannerite-B to -D all contain elevated ΣREY, with brannerite-B and -C having elevated As, and brannerite-D having elevated Nb.
All coffinite is typically globular (each globule is 2–10 μm in size) to collomorphic in appearance. Coffinite-A ranges from discrete globules to collomorphic bands completely encompassing quartz. Coffinite-B is always found with uraninite, and includes collomorph coffinite enveloped by massive uraninite, as well as aureoles of coffinite on the margins of uraninite crystals. Coffinite-C is associated with brannerite and REY minerals. The majority of coffinite is heterogeneous.
Brannerite and coffinite have probably precipitated as part of a late-stage hydrothermal U-event, which might have involved the dissolution and/or reprecipitation of earlier precipitated uraninite, or could represent the products of a later U mineralizing event. Evidence which supports formation of late-stage coffinite and brannerite includes: (1) low-Pb contents of both minerals; (2) coffinite is commonly found on the edges of uraninite, implying later deposition; and (3) coffinite is often found on the edge of brannerite aggregates, suggestive of brannerite precipitation occurred before coffinite. Moreover, there are many features (e.g. banding, scalloped edges, alteration rinds, variable compositions etc.) indicative of hydrothermal alteration processes.
Ore characterization and textural relationships among gold, selenides, platinum-group minerals and uraninite at the granite-related Buraco do Ouro gold mine, Cavalcante, Central Brazil
- J. Menez, N. F. Botelho
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- 02 January 2018, pp. 463-475
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Gold occurrences have been reported in the northeastern part of Goiás State since the beginning of the 18th Century. The main mineralization is associated with Paleoproterozoic peraluminous, syntectonic granites of the Aurumina Suite and associated metasedimentary,graphite-bearing country rocks of the Ticunzal Formation. In the Buraco do Ouro gold mine, the mineralization is hosted in muscovite-quartz mylonite in a silicified shear zone near the contact between biotite-muscovite granite and paragneiss of the Ticunzal Formation. The ore mineralogy consistsof gold, paraguanajuatite (Bi2Se3), kalungaite (PdAsSe), isomertieite [Pd11Sb2As2], mertieite II [Pd8(Sb,As)3], sperrylite (PtAs2), padmaite (PdBiSe), bohdanowiczite (AgBiSe2), clausthalite (PbSe),krutaite (CuSe2), ferroselite (FeSe2), uraninite (UO2) and unnamed Ag-Pb-Bi-Se minerals. Local magnetite concentrations and rare chalcopyrite and pyrite are also associated with both mineralized and barren mylonites in a gangue consisting of muscovite, quartzand rare tourmaline. High TiO2 muscovite clasts in the ore are interpreted as the magmatic muscovite of the original granite, and the mineralization is considered to be synchronous with the syntectonic granite intrusion during syn-emplacement shearing and alteration. The associationbetween granitic rocks and platinum-group element (PGE)-bearing gold mineralization observed in the Buraco do Ouro mine is uncommon and unique in the context of the Aurumina Suite and the Ticunzal Formation, where gold deposits and occurrences are gold-only. The chemical data suggest the possibilityof a solid solution between paraguanajuatite and bohdanowiczite. In addition, a complex intergrowth occurs between paraguanajuatite, clausthalite and Ag-Pb-Bi-Se phases, one of which, a Pb-Bi-Se phase could represent a new mineral. Uraninite is identified for the first time in this mineralassemblage and its concentration in the ore seems important, as revealed by high gamma spectrometric measurements in the samples collected in the mine. The association between gold and uranium constitutes a regional signature, observed in both gold and uranium deposits in the Cavalcante region.
First crystal-structure determination of natural lansfordite, MgCO3·5H2O
- Fabrizio Nestola, Anatoly V. Kasatkin, Sergey S. Potapov, Olga YA. Chervyatsova, Arianna Lanza
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- 02 January 2018, pp. 1063-1071
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This study presents the first crystal-structure determination of natural MgCO3·5H2O, mineral lansfordite, in comparison with previous structural works performed on synthetic analogues. A new prototype single-crystal X-ray diffractometer allowed us to measure an extremely small crystal (i.e. 0.020 mm × 0.010 mm × 0.005 mm) and refine anisotropically all non-hydrogen atoms in the structure and provide a robust hydrogen-bond arrangement. Our new data confirm that natural lansfordite can be stable for several months at room temperature, in contrast with previous works, which reported that such a mineral could be stable only below 10°C.
On the nature and origin of garnet in highly-refractory Archean lithospheric mantle: constraints from garnet exsolved in Kaapvaal craton orthopyroxenes
- Sally A. Gibson
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- 02 January 2018, pp. 781-809
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The widespread occurrence of pyrope garnet in Archean lithospheric mantle remains one of the 'holy grails' of mantle petrology. Most garnets found in peridotitic mantle equilibrated with incompatible-trace-element enriched melts or fluids and are the products of metasomatism. Less common are macroscopic intergrowths of pyrope garnet formed by exsolution from orthopyroxene. Spectacular examples of these are preserved in both mantle xenoliths and large, isolated crystals (megacrysts) from the Kaapvaal craton of southern Africa, and provide direct evidence that some garnet inthe sub-continental lithospheric mantle formed initially by isochemical rather than metasomatic processes. The orthopyroxene hosts are enstatites and fully equilibrated with their exsolved phases (low-Cr pyrope garnet ± Cr-diopside). Significantly, P-T estimates of the postexsolution orthopyroxenes plot along an unperturbed conductive Kaapvaal craton geotherm and reveal that they were entrained from a large continuous depth interval (85 to 175 km). They therefore represent snapshots of processes operating throughout almost the entire thickness of the sub-cratonic lithosphericmantle.
New rare-earth element (REE) analyses show that the exsolved garnets occupy the full spectrum recorded by garnets in mantle peridotites and also diamond inclusions. A key finding is that a few low-temperature exsolved garnets, derived from depths of ∼90 km, are more depleted in light rare-earth elements (LREEs) than previously observed in any other mantle sample. Importantly, the REE patterns of these strongly LREE-depleted garnets resemble the hypothetical composition proposed for pre-metasomatic garnets that are thought to pre-date major enrichment events in the sub-continental lithospheric mantle, including those associated with diamond formation. The recalculated compositions of pre-exsolution orthopyroxenes have higher Al2O3 and CaO contents than their post-exsolution counterparts and most probably formed as shallow residues of large amounts of adiabatic decompression melting in the spinel-stability field. It is inferred that exsolution of garnet from Kaapvaal orthopyroxenes may have been widespread, and perhaps accompanied cratonization at ∼2.9 to 2.75 Ga. Such a process would considerably increase the density and stability of the continental lithosphere.
Rare-earth mobility as a result of multiple phases of fluid activity in fenite around the Chilwa Island Carbonatite, Malawi
- Emma Dowman, Frances Wall, Peter J. Treloar, Andrew H. Rankin
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- 26 January 2018, pp. 1367-1395
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Carbonatites are enriched in critical raw materials such as the rare-earth elements (REE), niobium, fluorspar and phosphate. A better understanding of their fluid regimes will improve our knowledge of how to target and exploit economic deposits. This study shows that multiple fluid phases penetrated the surrounding fenite aureole during carbonatite emplacement at Chilwa Island, Malawi. The first alkaline fluids formed the main fenite assemblage and later microscopic vein networks contain the minerals of potential economic interest such as pyrochlore in high-grade fenite and rare-earth minerals throughout the aureole. Seventeen samples of fenite rock from the metasomatic aureole around the Chilwa Island carbonatite complex were chosen for study. In addition to the main fenite assemblage of feldspar and aegirine ± arfvedsonite, riebeckite and richterite, the fenite contains micro-mineral assemblages including apatite, ilmenite, rutile, magnetite, zircon, rare-earth minerals and pyrochlore in vein networks. Petrography using a scanning electron microscope in energy-dispersive spectroscopy mode showed that the rare-earth minerals (monazite, bastnäsite and parisite) formed later than the fenite feldspar, aegirine and apatite and provide evidence of REE mobility into all grades of fenite. Fenite apatite has a distinct negative Eu anomaly (determined by laser ablation inductively coupled plasma mass spectrometry) that is rare in carbonatite-associated rocks and interpreted as related to pre-crystallization of plagioclase and co-crystallization with K-feldspar in the fenite. The fenite minerals have consistently higher mid REE/light REE ratios (La/Sm ≈ 1.3 monazite, ≈ 1.9 bastnäsite, ≈ 1.2 parisite) than their counterparts in the carbonatites (La/Sm ≈ 2.5 monazite, ≈ 4.2 bastnäsite, ≈ 3.4 parisite). Quartz in the low- and medium-grade fenite hosts fluid inclusions, typically a few micrometres in diameter, secondary and extremely heterogeneous. Single phase, 2- and 3-phase, single solid and multi solid-bearing examples are present, with 2-phase the most abundant. Calcite, nahcolite, burbankite and baryte were found in the inclusions. Decrepitation of inclusions occurred at ∼200°C before homogenization but melting-temperature data indicate that the inclusions contain relatively pure CO2. A minimum salinity of ∼24 wt.% NaCl equivalent was determined. Among the trace elements in whole-rock analyses, enrichment in Ba, Mo, Nb, Pb, Sr, Th and Y and depletion in Co, Hf and V are common to carbonatite and fenite but enrichment in carbonatitic type elements (Ba, Nb, Sr, Th, Yand REE) generally increases towards the inner parts of the aureole. A schematic model contains multiple fluid events, related to first and second boiling of the magma, accompanying intrusion of the carbonatites at Chilwa Island, each contributing to the mineralogy and chemistry of the fenite. The presence of distinct rare-earth mineral microassemblages in fenite at some distance from carbonatite could be developed as an exploration indicator of REE enrichment.
Kyawthuite, Bi3+Sb5+O4, a new gem mineral from Mogok, Burma (Myanmar)
- Anthony R. Kampf, George R. Rossman, Chi Ma, Peter A. Williams
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- 02 January 2018, pp. 477-484
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Kyawthuite, Bi3+Sb5+O4, is a new gem mineral found as a waterworn crystal in alluvium at Chaung-gyi-ah-le-ywa in the Chaung-gyi valley, near Mogok, Burma (Myanmar). Its description is based upon a single sample, which was faceted into a 1.61-carat gem.The composition suggests that the mineral formed in a pegmatite. Kyawthuite is monoclinic, space group I2/c, with unit cell dimensions a = 5.4624(4), b = 4.88519(17), c = 11.8520(8) Å, β = 101.195(7)°, V = 310.25(3) Å3and Z = 4. The colour is reddish orange and the streak is white. It is transparent with adamantine lustre. The Mohs hardness is 5½. Kyawthuite is brittle with a conchoidal fracture and three cleavages: {001} perfect, {110} and {110} good. The measured density is 8.256(5) g cm–3and the calculated density is 8.127 g cm–3. The mineral is optically biaxial with 2V = 90(2)°. The predicted indices of refraction are α = 2.194, β = 2.268, γ = 2.350. Pleochroism is imperceptible and the optical orientation is X = b; Y≈ c; Z ≈ a. Electron microprobe analyses, provided the empirical formula (Bi0.823+Sb0.183+)∑1.00(Sb0.995+Ta0.015+)∑1.00O4. The Raman spectrumis similar to that of synthetic Bi3+Sb5+O4. The infrared spectrum shows a trace amount of OH/H2O. The eight strongest powder X-ray diffraction lines are [dobs in Å(I)(hkl)]: 3.266(100)(112), 2.900(66)(112), 2.678(24)(200), 2.437(22)(020,114), 1.8663(21)(024), 1.8026(43)(116,220,204), 1.6264(23)(224,116) and 1.5288(28)(312,132). In the crystal structure of kyawthuite (R1 = 0.0269 for 593 reflections with Fo > 4σF), Sb5+O6 octahedrashare corners to form chequerboard-like sheets parallel to {001}. Atoms of Bi3+, located above and below the open squares in the sheets, form bonds to the O atoms in the sheets, thereby linking adjacent sheets into a framework. The Bi3+ atom is in lopsided 8 coordination,typical of a cation with stereoactive lone electron pairs. Kyawthuite is isostructural with synthetic β-Sb2O4 and clinocervantite (natural β-Sb2O4).