Volume 79 - Issue 3 - June 2015
Research Article
Experimental evidence for partial Fe2+ disorder at the Y and Z sites of tourmaline: a combined EMP, SREF, MS, IR and OAS study of schorl
- Ferdinando Bosi, Giovanni B. Andreozzi, Ulf Hålenius, Henrik Skogby
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- 02 January 2018, pp. 515-528
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An experimental study of an Al-rich schorl sample from Cruzeiro mine (Minas Gerais, Brazil) was carried out using electron microprobe analysis, structural refinement and Mössbauer, infrared and optical absorption spectroscopy in order to explore the disordering of Fe2+ over the Y and Z sites of the tourmaline structure.
A structural formula was obtained by merging chemical and structural data. The cation distribution at the two non-equivalent octahedrally coordinated sites (Y and Z) was obtained by two different optimization procedures which, minimizing the residuals between observed and calculated data, converged to the formula: X(Na0.65〈0.32Ca0.02K0.01)Σ1.00Y(Fe1.652+Al1.15Fe0.063+Mn0.052+Zn0.05Ti0.044+)Σ3.00Z(Al5.52Fe0.302+Mg0.18)Σ6.00[T(Si5.87Al0.13)Σ6.00O18](BBO3)3V(OH)3W[(OH)0.34F0.28O0.38]Σ1.00.
This result shows a partial disordering of Fe2+ over the Y and Z sites which explains adequately the mean atomic number observed for the Z site (13.5±0.1). Such a disordering is also in line with the shoulder recorded in the Mössbauer spectrum (fitted by a doublet with isomer shift of 1.00 mm/s and quadrupole splitting of 1.38 mm/s) as well as with the asymmetric bands recorded in the optical absorption spectrum at ∼9000 and 14,500 cm–1 (modelled by four Gaussian bands, centred at 7677 and 9418 cm–1, and 13,154 and 14,994 cm–1, respectively).
The high degree of consistency in the results obtained using the different methods suggests that the controversy over Fe2+ order can be ascribed to the failure to detect small amounts of Fe2+ at Z (typically <<10% atoms/site) rather than a steric effect of Fe2+ on the tourmaline structure.
IMA Commission on New Minerals, Nomenclature and Classification (CNMNC) Newsletter 25
CNMNC Newsletter
New minerals and nomenclature modifications approved in 2015
- U. Hålenius, F. Hatert, M. Pasero, S. J. Mills
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- 02 January 2018, pp. 529-535
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Research Article
Stabilities of byströmite, MgSb2O6, ordoñezite, ZnSb2O6 and rosiaite, PbSb2O6, and their possible roles in limiting antimony mobility in the supergene zone
- Adam J. Roper, Peter Leverett, Timothy D. Murphy, Peter A. Williams
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- 02 January 2018, pp. 537-544
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In order to clarify the roles that secondary minerals may have in determining the extent of dispersion of Sb in the supergene environment, syntheses and stability studies of the Sb(V) oxides byströmite, MgSb2O6, ordoñezite, ZnSb2O6 and rosiaite, PbSb2O6, have been undertaken. Solubilities in aqueous HNO3 were determined at 298.2 K and the data obtained used to calculate values of Δ at the same temperature. The derived Δ(s, 298.2 K) values for MgSb2O6 (–1554.1 ±3.6 kJ mol–1), ZnSb2O6 (–1257.0 ±2.6 kJ mol–1) and PbSb2O6 (–1154.2 ±2.6 kJ mol–1) have been used in subsequent calculations to determine their relative stabilities and relationships with other secondary Sb minerals.
Corundum (sapphire) and zircon relationships, Lava Plains gem fields, NE Australia: Integrated mineralogy, geochemistry, age determination, genesis and geographical typing
- F. L. Sutherland, R. R. Coenraads, A. Abduriyim, S. Meffre, P. W. O. Hoskin, G. Giuliani, R. Beattie, R. Wuhrer, G. B. Sutherland
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- 02 January 2018, pp. 545-581
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Gem minerals at Lava Plains, northeast Queensland, offer further insights into mantle-crustal gemformation under young basalt fields. Combined mineralogy, U-Pb age determination, oxygen isotope and petrological data on megacrysts and meta-aluminosilicate xenoliths establish a geochemical evolution in sapphire, zircon formation between 5 to 2 Ma. Sapphire megacrysts with magmatic signatures (Fe/Mg ∼100–1000, Ga/Mg 3–18) grew with ∼3 Ma micro-zircons of both mantle (δ18O 4.5–5.6%) and crustal (δ18O 9.5–10.1‰) affinities. Zircon megacrysts (3±1 Ma) show mantle and crustal characteristics, but most grew at crustal temperatures (600–800°C). Xenolith studies suggest hydrous silicate melts and fluids initiated from amphibolized mantle infiltrated into kyanite+sapphire granulitic crust (800°C, 0.7 GPa). This metasomatized the sapphire (Fe/Mg ∼50–120, Ga/Mg ∼3–11), left relict metastable sillimanite-corundum-quartz and produced minerals enriched in high field strength, large ion lithophile and rare earth elements. The gem suite suggests a syenitic parentage before its basaltic transport. Geographical trace-element typing of the sapphire megacrysts against other eastern Australian sapphires suggests a phonolitic involvement.
Flamite, (Ca,Na,K)2(Si,P)O4, a new mineral from ultrahightemperature combustion metamorphic rocks, Hatrurim Basin, Negev Desert, Israel
- E. V. Sokol, Y. V. Seryotkin, S. N. Kokh, Ye. Vapnik, E. N. Nigmatulina, S. V. Goryainov, E. V. Belogub, V. V. Sharygin
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- 02 January 2018, pp. 583-596
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Flamite (Ca,Na,K)2(Si,P)O4 (P63; a = 43.3726(18), c = 6.8270(4) Å; V = 11122.2(9) Å3), a natural analogue of the P,Na,K-doped high-temperature α-Ca2SiO4 modification, is a new mineral from Ca- and Al-rich paralava, an ultrahigh-temperature combustion metamorphic melt rock. The type locality is situated in the southern Hatrurim Basin, the Negev Desert, Israel. Flamite occurs as regular lamellar intergrowths with partially hydrated larnite, together with rock-forming gehlenite, rankinite and Ti-rich andradite, minor ferrian perovskite, magnesioferrite, hematite, and retrograde ettringite and calcium silicate hydrates. The mineral is greyish to yellowish, transparent with a vitreous lustre, non-fluorescent under ultraviolet light and shows no parting or cleavage; Mohs hardness is 5–5½; calculated density is 3.264 g cm–3. The empirical formula of holotype flamite (mean of 21 analyses) is (Ca1.82Na0.09K0.06(Mg,Fe,Sr,Ba)0.02)Σ1.99(Si0.82P0.18)Σ1.00O4. The strongest lines in the powder X-ray diffraction pattern are [d, Å (Iobs)]: 2.713(100), 2.765(44), 2.759(42), 1.762(32), 2.518(29), 2.402(23), 2.897(19), 1.967(18), 2.220(15), 1.813(15). The strongest bands in the Raman spectrum are 170, 260, 520, 538, 850, 863, 885, 952 and 1003 cm–1.
The crystal structure of balićžunićite, Bi2O(SO4)2, a new natural bismuth oxide sulfate
- Daniela Pinto, Anna Garavelli, Tonci Balić-Žunić
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- 02 January 2018, pp. 597-611
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The crystal structure of balićžunićite, Bi2O(SO4)2, a new mineral species from the La Fossa crater of Vulcano (Aeolian Islands, Italy), was solved from single-crystal X-ray diffraction data and refined to R = 0.0507. The structure is triclinic, space group P1, with a = 6.7386(3), b = 11.1844(5), c = 14.1754(7) Å, α = 80.082(2), β = 88.462(2)°, γ = 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The crystal structure consists of six independent Bi sites, six S sites and 27 O sites of which three are oxo oxygen atoms not bonded to sulfur. Bismuth and S atoms are arranged close to a eutectic pattern parallel to the (100) plane. The planes are stacked atom on atom such that Bi always overlays S and vice versa. This structural feature is shared with the known structure of the high-temperature polymorph of the same compound, stable at T >535°C. However, the sequences of Bi and S atoms in the two structures are different and so are the arrangements of oxygen atoms. Characteristic building blocks in the structure of balićžunićite are clusters of five Bi atoms which form nearly planar trapezoidal Bi5 groups with oxo oxygens located in the centres of the three Bi3 triangles, which form the trapezoids. The trapezoidal Bi5O39+ ions are joined along [100] with SO42– groups by means of strong bismuth-sulfate oxygen bonds, forming infinite [100] rods with composition Bi5O3(SO4)5–. One sixth of the Bi atoms do not participate in trapezoids, but form, with additional SO42– groups, rows of composition BiSO4+, also parallel to [100]. [Bi5O3(SO4)5–] rods form infinite layers parallel to (010) with [BiSO4+] rows located on the irregular surface of contact between adjacent layers. Bi atoms occur in four different coordination types, all showing the stereochemical influence of the Bi3+ lone electron pair. In this respect the crystal structure of balićžunićite shows greater variability than its high-temperature polymorph which has only two types of the Bi coordination spheres present in balićžunićite.
Shilovite, natural copper(II) tetrammine nitrate, a new mineral species
- Nikita V. Chukanov, Sergey N. Britvin, Gerhard Möhn, Igor V. Pekov, Natalia V. Zubkova, Fabrizio Nestola, Anatoly V. Kasatkin, Maurizio Dini
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- 02 January 2018, pp. 613-623
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The new mineral shilovite, the first natural tetrammine copper complex, was found in a guano deposit located on the Pabellón de Pica Mountain, near Chanabaya, Iquique Province, Tarapacá Region, Chile. It is associated with halite, ammineite, atacamite (a product of ammineite alteration) and thénardite. The gabbro host rock consists of amphibole, plagioclase and minor clinochlore, and contains accessory chalcopyrite. The latter is considered the source of Cu for shilovite. The new mineral occurs as deep violet blue, imperfect, thick tabular to equant crystals up to 0.15 mm in size included in massive halite. The mineral is sectile. Its Mohs hardness is 2. Dcalc is 1.92 g cm–3. The infrared spectrum shows the presence of NH3 molecules and NO3– anions. Shilovite is optically biaxial (+), α = 1.527(2), β = 1.545(5), γ = 1.610(2). The chemical composition (electron-microprobe data, H calculated from ideal formula, wt.%) is Cu 26.04, Fe 0.31, N 30.8, O 35.95, H 4.74, total 100.69. The empirical formula is H12.56(Cu1.09Fe0.01)N5.87O6.00. The idealized formula is Cu(NH3)4(NO3)2. The crystal structure was solved and refined to R = 0.029 based upon 2705 unique reflections having F > 4σ(F). Shilovite is orthorhombic, space group Pnn2, a = 23.6585(9), b = 10.8238(4), c = 6.9054(3) Å, V = 1768.3(1) Å3, Z = 8. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are: 5.931 (41) (400), 5.841 (100) (011), 5.208 (47) (410), 4.162 (88) (411), 4.005 (62) (420), 3.462 (50) (002), 3.207 (32) (031), 2.811 (40) (412).
Gatedalite, Zr(Mn2+2Mn3+4)SiO12, a new mineral species of the braunite group from Långban, Sweden
- Ulf Hålenius, Ferdinando Bosi
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- 02 January 2018, pp. 625-634
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Gatedalite, Zr(Mn22+Mn43+)SiO12, is a new mineral of the braunite group. It is found in hausmannite-impregnated skarn together with jacobsite, Mn-bearing calcite, tephroite, Mn-bearing phlogopite, långbanite, pinakiolite and oxyplumboroméite at the Långban Mn-Fe oxide deposit, Värmland, central Sweden. The mineral occurs as very rare, small (≤60 μm), grey, submetallic, irregularly rounded anhedral grains. Gatedalite has a calculated density of 4.783 g/cm3. It is opaque and weakly anisotropic with reflectivity in air varying between 17.1 and 20.8% in the visible spectral range. Gatedalite is tetragonal, space group I41/acd, with the unit-cell parameters a = 9.4668(6) Å, c = 18.8701(14) Å, V = 1691.1(2) Å3 and Z = 8. The crystal structure was refined to an R1 index of 5.09% using 1339 unique reflections collected with MoKαX-ray radiation. The five strongest powder X-ray diffraction lines [d in Å, (I), (hkl)] are: 2.730(100)(224), 2.367(12)(040), 1.6735(12)(440), 1.6707(29)(048) and 1.4267(16)(264). Electron microprobe analyses in combination with single-crystal structure refinement resulted in the empirical formula: (Zr0.494+Mn0.402+Mg0.07Ca0.02Zn0.01Ce0.013+)Σ1.00(Mn4.443+Fe0.593+Mn0.572+Mg0.41Al0.01)Σ6.02Si0.99O12. Gatedalite is a member of the braunite group (general formula AB6SiO12). It is related to braunite (Mn2+Mn63+SiO12) through the net cation exchange (Zr4+ + Mn2+) → 2Mn3+, which results from the substitutions Zr4+ → Mn2+ at the 8-fold coordinated site (A in the general formula) coupled with a 2Mn2+ → 2Mn3+ substitution at the 6-fold coordinated sites (B in the general formula).
Manganese incorporation in synthetic hercynite
- G. D. Bromiley, G. D. Gatta, T. Stokes
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- 02 January 2018, pp. 635-647
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Manganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an fO2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of fO2 conditions in magmas during spinel crystallization.
New crystal-chemical data for marécottite
- J. Plášil, R. Škoda
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- 02 January 2018, pp. 649-660
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Marécottite, ideally Mg3[(UO2)4O3(OH)(SO4)2]2(H2O)28, a triclinic, Mg-dominant member of the zippeite group, was described originally from a small uranium deposit at La Creusaz in Wallis (Switzerland). It has recently been found at Jáchymov (Czech Republic), where it forms exceptional crystals, up to 0.3 mm across. According to an electron microprobe study of these crystals, marécottite from Jáchymov is chemically similar to the material from the La Creusaz deposit. However, the Jáchymov crystals exhibit more cation substitution (Zn2+ and Mn2+ for Mg2+). The chemical composition of marécottite from Jáchymov corresponds to the empirical formula [(Na0.05K0.07)Σ0.12(Mg1.83Zn0.41Mn0.41Cu0.15Ni0.08)Σ2.88Al0.07]Σ3.07(UO2)8[(SO4)3.77(SiO4)0.21]Σ3.98O6(OH)1.84·28H2O (the mean of four representative spots; calculated on the basis of eight U atoms and 28 H2O per formula unit and 1.84 OH for charge balance). According to single-crystal X-ray diffraction, marécottite from Jáchymov is triclinic, P1, a = 10.8084(2), b = 11.2519(3), c = 13.8465(3) Å, α = 66.222(2), β = 72.424(2), γ = 70.014(2)o, V = 1421.57(6) Å3 and Z = 1. The crystal structure was refined from a highly redundant dataset (30,491 collected reflections) to R1 = 0.0367 for all 7042 unique reflections. The refined structure confirms the previously determined structure for the crystal from the La Creusaz deposit. An extensive network of hydrogen bonds is an important feature that keeps the whole structure together, but the positions of H atoms had not been determined previously. The H-bond scheme proposed based on a detailed bond-valence analysis and the role of different types of molecular H2O in the structure is discussed.
Ferribushmakinite, Pb2Fe3+(PO4)(VO4)(OH), the Fe3+ analogue of bushmakinite from the Silver Coin mine, Valmy, Nevada
- A. R. Kampf, P. M. Adams, B. P. Nash, J. Marty
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- 02 January 2018, pp. 661-669
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Ferribushmakinite (IMA2014-055), Pb2Fe3+(PO4)(VO4)(OH), the Fe3+ analogue of bushmakinite, is a new mineral from the Silver Coin mine, Valmy, Iron Point district, Humboldt County, Nevada, USA, where it occurs as a low-temperature secondary mineral in association with plumbogummite, mottramite, Br-rich chlorargyrite and baryte on massive quartz. Ferribushmakinite forms yellow slightly flattened prisms up to 0.2 mm long growing in X and sixling twins. The streak is pale yellow. Crystals are translucent and have adamantine lustre. The Mohs hardness is ∼2, the tenacity is brittle, the fracture is irregular to splintery and crystals exhibit one or two fair cleavages in the [010] zone. The calculated density is 6.154 g/cm3. Electron microprobe analyses provided: PbO 63.69, CaO 0.07, CuO 1.11, Fe2O3 7.63, Al2O3 1.63, V2O5 12.65, As2O5 3.09, P2O58.63, H2O 1.50 (structure), total 100.00 wt.% (normalized). The empirical formula (based on nine O a.p.f.u.) is: (Pb1.99Ca0.01)Σ2.00(Fe0.66Al0.22Cu0.10)Σ0.98(V0.97P0.85As0.19)Σ2.01O7.84(OH)1.16. Ferribushmakinite is monoclinic, P21/m, a = 7.7719(10), b = 5.9060(7), c = 8.7929(12) Å, β = 111.604(8)°, V = 375.24(9) Å3 and Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [dobs in Å (I)(hkl)]: 4.794(46)(011); 3.245(84)(211); 2.947(100)(020,212,103); 2.743(49)(112); 2.288(30)(220); 1.8532(27)(314,403); 1.8084(27)(multiple); and 1.7204(28)(312,114,321). Ferribushmakinite is a member of the brackebuschite supergroup. Its structure (R1 = 3.83% for 577 Fo > 4σF) differs from that of bushmakinite only in the dominance of Fe3+ over Al in the octahedral site.
Barrydawsonite-(Y), Na1.5CaY0.5Si3O9H: a new pyroxenoid of the pectolite–serandite group
- R. H. Mitchell, M. D. Welch, A. R. Kampf, A. K. Chakhmouradian, J. Spratt
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- 02 January 2018, pp. 671-686
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The new pyroxenoid barrydawsonite-(Y) occurs at the Merlot Claim, North Red Wine Pluton, Labrador, Canada (62°32'38.54'' W; 54°08'1.37'' N). The host rock is a metamorphosed eudialyte syenite consisting of eudialyte, potassic arfvedsonite, jadeitic aegirine, nepheline, albite and potassium feldspar with accessory Y-bearing pectolite, britholite and steenstrupine. Barrydawsonite-(Y) crystals commonly have discrete thin rims of Y-bearing pectolite. The average empirical formula (based on nine anions p.f.u.) is Na1.54Ca0.74Mn0.15Fe0.07Y0.38Nd0.01Sm0.01Gd0.02Tb0.01Dy0.04Ho0.01Er0.02Yb0.01Si3.00O9H. The simplified formula is Na1.5Y0.5CaSi3O9H. Barrydawsonite-(Y) is related to pectolite by the substitution ½[NaM3+Ca–2] (M3+ = Y,REE), and is exceptional in being the only member of the pectolite group that has the structure of the monoclinic M2abc polytype. The crystal structure has been determined in monoclinic space group P21/a: a = 15.5026(2), b = 7.0233(1), c = 6.9769(1) Å, β = 95.149(1)°, V = 756.58(2) Å3(Z = 4). Final agreement indices are R1 = 0.038, wR2 = 0.068, Goof = 1.136. The asymmetric unit of barrydawsonite-(Y) has three metal sites: M(1) = Ca, M(2) = Na0.5(Y,REE)0.5, M(3) = Na. M(1) and M(2) are octahedrally-coordinated sites, whereas M(3) is [8]-coordinated as in pectolite and serandite. The structural formula for the empirical composition is M(3)Na1.00M(2)(Na0.50Y0.38REE0.13)Σ=1.01M(1)(Na0.04Ca0.74Mn0.152+Fe0.072+)Σ=1.00Si3O9H. There is excellent agreement between the refined site-scattering values and those calculated based upon the structural formula.
Barrydawsonite-(Y) is biaxial (+) with α = 1.612(1), β = 1.617(1), γ = 1.630(1) (white light) and 2V = 63(1)°. The five strongest peaks in the X-ray powder diffraction pattern are [dobs (Å), Iobs%, (hkl)]: [2.905, 100, (023)], [3.094, 30, (210,211,121,202)], [1.7613, 29, (127,323,040)], [3.272, 27, (202,104)], [1.7016, 27, (140,227,325)].
Eckerite, Ag2CuAsS3, a new Cu-bearing sulfosalt from Lengenbach quarry, Binn valley, Switzerland: description and crystal structure
- L. Bindi, F. Nestola, S. Graeser, P. Tropper, T. Raber
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- 02 January 2018, pp. 687-694
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Eckerite, ideally Ag2CuAsS3, is a new mineral from the Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs as very rare euhedral crystals up to 300 μm across associated with realgar, sinnerite, hatchite, trechmannite and yellow, fibrous smithite. In thick section eckerite is opaque with a metallic lustre and shows a dark orange-red streak. It is brittle; the Vickers hardness (VHN25) is 70 kg/mm2 (range: 64–78) (Mohs hardness of ∼2½–3). In reflected light, eckerite is moderately bireflectant and weakly pleochroic from light grey to a slightly bluish grey. Internal reflections are absent. Under crossed nicols, it is weakly anisotropic with greyish to light blue rotation tints. Reflectance percentages for Rmin and Rmax are 27.6, 31.7 (471.1 nm), 22.8, 26.1 (548.3 nm), 21.5, 24.5 (586.6 nm) and 19.4, 22.3 (652.3 nm), respectively.
Eckerite is monoclinic, space group C2/c, with a = 11.8643(3), b = 6.2338(1), c = 16.6785(4) Å, β = 110.842(3)°, V = 1152.81(5) Å3, Z = 8. The crystal structure [R1 = 0.0769 for 1606 reflections with Fo > 4σ(Fo)] is topologically identical to that of xanthoconite and pyrostilpnite. In the structure, AsS3 pyramids are joined by AgS3 triangles to form double sheets parallel to (001); the sheets are linked by Cu(Ag) atoms in a quasi-tetrahedral coordination. Among the three metals sites, Ag2 is dominated by Cu. The mean metal–S distances reflect well the Ag ↔ Cu substitution occurring at this site.
The eight strongest powder X-ray diffraction lines [d in Å (I/I0) (hkl)] are: 3.336 (70) (312); 2.941 (100) (314,114); 2.776 (80) (400,206); 2.677 (40) (312); 2.134 (50) (421); 2.084 (40) (208,206); 2.076 (40) (420); 1.738 (40) (228,226). A mean of five electron microprobe analyses gave Ag 52.08(16), Cu 11.18(9), Pb 0.04(1), Sb 0.29(3), As 15.28(11), S 20.73(13), total 99.60 wt.%, corresponding, on the basis of a total of 7 atoms per formula unit, to Ag2.24Cu0.82As0.94Sb0.01S2.99. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (2014–063) and named for Markus Ecker, a well known mineral expert on the Lengenbach minerals for more than 25 years.
Bobcookite, NaAl(UO2)2(SO4)4·18H2O and wetherillite, Na2Mg(UO2)2(SO4)4·18H2O, two new uranyl sulfate minerals from the Blue Lizard mine, San Juan County, Utah, USA
- Anthony R. Kampf, Jakub Plášil, Anatoly V. Kasatkin, Joe Marty
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- 02 January 2018, pp. 695-714
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The new minerals bobcookite (IMA 2014-030), NaAl(UO2)2(SO4)4·18H2O and wetherillite (IMA 2014-044), Na2Mg(UO2)2(SO4)4·18H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with boyleite, chalcanthite, dietrichite, gypsum, hexahydrite, johannite, pickeringite and rozenite.
Bobcookite descriptive details: lime green to greenish-yellow massive veins and columnar crystals; transparent; vitreous lustre; bright greenish-white fluorescence; pale greenish yellow streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; moderately hygroscopic; easily soluble in cold H2O; densitycalc = 2.669 g cm–3. Optically, biaxial (–), α = 1.501(1), β = 1.523(1), γ = 1.536(1) (white light); 2Vmeas. = 78(1)°; 2Vcalc. = 74°; dispersion r < v, moderate. Pleochroism: X colourless, Y very pale yellow-green, Z pale yellow-green; X < Y < Z. EDS analyses yielded the empirical formula Na0.97Al1.09(U1.02O2)2(S0.98O4)4(H2O)18. Bobcookite is triclinic, P1, a = 7.7912(2), b = 10.5491(3), c = 11.2451(8) Å , α = 68.961(5), β = 70.909(5), γ = 87.139(6)°, V = 812.79(8) Å3 and Z = 1. The structure (R1 = 1.65% for 3580 Fo > 4σF) contains [(UO2)(SO4)2(H2O)] chains linked by NaO4(H2O)2 octahedra to form layers. Hydrogen bonds to insular Al(H2O)6 octahedra and isolated H2O groups hold the structure together. The mineral is named for Dr Robert (Bob) B. Cook of Auburn University, Alabama, USA.
Wetherillite descriptive details: pale greenish-yellow blades; transparent; vitreous lustre; white streak; hardness (Mohs) 2; brittle; two cleavages, {101} perfect and {010} fair; conchoidal or curved fracture; easily soluble in cold H2O; densitycalc = 2.626 g cm–3. Optically, biaxial (+), α = 1.498(1), β = 1.508(1), γ = 1.519(1) (white light); 2Vmeas. = 88(1)°, 2Vcalc. = 87.9°; dispersion is r < v, distinct; optical orientation: Z = b, X ∧ a = 54° in obtuse β; pleochroism: X colourless, Y pale yellow-green, Z pale yellow-green; X < Y ≈ Z. EDS analyses yielded the empirical formula Na1.98(Mg0.58Zn0.24Cu0.11Fe0.092+)Σ1.02(U1.04O2)2(S0.98O4)4(H2O)18. Wetherillite is monoclinic, P21/c, a = 20.367(1), b = 6.8329(1), c = 12.903(3) Å, β = 107.879(10)°, V = 1709.0(5) Å3 and Z = 2. The structure (R1 = 1.39% for 3625 Fo > 4σF) contains [(UO2)(SO4)2(H2O)] sheets parallel to {100}. Edge-sharing chains of Na(H2O)5O polyhedra link adjacent uranyl sulfate sheets forming a weakly bonded three-layer sandwich. The sandwich layers are linked to one another by hydrogen bonds through insular Mg(H2O)6 octahedra and isolated H2O groups. The mineral is named for John Wetherill (1866–1944) and George W. Wetherill (1925–2006).
Kerimasite, {Ca3}[Zr2](SiFe3+2)O12 garnet from the Vysoká-Zlatno skarn, Štiavnica stratovolcano, Slovakia
- Pavel Uher, Stanislava Milovská, Rastislav Milovský, Peter Koděra, Peter Bačík, Vladimír Bilohuščin
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- 02 January 2018, pp. 715-733
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Kerimasite {Ca3}[Zr2](SiFe23+)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 skarn-porphyry 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 dissolution-reprecipitation. 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 ≈ 700°C and P ≈ 50–70 MPa.
Ferriakasakaite-(La) and ferriandrosite-(La): new epidote-supergroup minerals from Ise, Mie Prefecture, Japan
- Mariko Nagashima, Daisuke Nishio-Hamane, Norimitsu Tomita, Tetsuo Minakawa, Sachio Inaba
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- 02 January 2018, pp. 735-753
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The new REE-rich, monoclinic, epidote-supergroup minerals ferriakasakaite-(La) and ferriandrosite-(La), found in tephroite calcite veinlets cutting the stratiform ferromanganese deposit from the Shobu area, Ise City, Mie Prefecture, Japan, were studied using electron microprobe analysis and single-crystal X-ray diffraction methods. Ferriakasakaite-(La), ideally A1CaA2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), has a new combination of dominant cations at A1(Ca) and M3(Mn2+), which are the key sites to determine a root name for epidote-supergroup minerals. The unit-cell parameters are a = 8.8733(2), b = 5.7415(1), c = 10.0805(3) Å, β = 113.845(2)° and V = 469.73(2) Å3. According to the structural refinement (R1 = 3.13%), the determined structural formula is A1(Ca0.54Mn2+0.46)A2[(La0.48Ce0.20Pr0.07Nd0.18Gd0.02)Σ0.95Ca0.05]M1(Fe0.423+V0.343+Al0.18Ti0.064+)M2(Al0.96Fe0.043+)M3(Mn0.502+Fe0.432+Mg0.07)(SiO4)(Si2O7)O(OH). Ferriandrosite-(La), ideally A1Mn2+A2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), is the M1Fe3+ analogue of androsite. The unit-cell parameters are a = 8.8779(1), b = 5.73995(1), c = 10.0875(2) Å, β = 113.899(1)° and V = 469.97(2) Å3, and the structural formula is A1(Mn0.562+Ca0.44)A2[(La0.49Ce0.20Pr0.08Nd0.19Gd0.02)Σ0.97Ca0.03]M1(Fe0.403+V0.283+Al0.20Fe0.052+Ti0.074+)M2(Al0.97Fe0.033+)M3(Mn0.502+Fe0.402+Mg0.10)(SiO4)(Si2O7)O(OH) (R1 = 2.93%). The two new minerals, which are compositionally very similar overall, are distinguished by occupancy of A1, Ca vs. Mn2+. The structural properties of these minerals depend not only on the REE content at A2, but also on the Mn content at A1.
First crystal-structure determination of chromites from an acapulcoite and ordinary chondrites
- Davide Lenaz, Francesco Princivalle, Birger Schmitz
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- 02 January 2018, pp. 755-765
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We report the first crystal-structure determinations of chromites from an acapulcoite and from ordinary chondrites. Cell edges range from 8.3212 (3) to 8.3501 (1) Å, while the oxygen positional parameters are in the range 0.2624 (3) to 0.26298 (9). Their compositions show they are very close to the chromite end-member FeCr2O4 with limited Al and Mg content. Titanium oxide content exceeds 1 wt.%, whereas the amount of Fe3+ is negligible. Extraterrestrial chromite is distinguished readily from terrestrial analogues on the basis of the cell edge and oxygen positional parameter. These distinctions will facilitate ongoing attempts to reconstruct the palaeoflux of meteorites to Earth from resistant extraterrestrial spinel grains recovered from ancient sediments.
Waimirite-(Y), orthorhombic YF3, a new mineral from the Pitinga mine, Presidente Figueiredo, Amazonas, Brazil and from Jabal Tawlah, Saudi Arabia: description and crystal structure
- Daniel Atencio, Artur C. Bastos Neto, Vitor P. Pereira, José T. M. M. Ferron, M. Hoshino, T. Moriyama, Y. Watanabe, R. Miyawaki, José M. V. Coutinho, Marcelo B. Andrade, Kenneth Domanik, Nikita V. Chukanov, K. Momma, H. Hirano, M. Tsunematsu
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- 02 January 2018, pp. 767-780
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Waimirite-(Y) (IMA 2013-108), orthorhombic YF3, occurs associated with halloysite, in hydrothermal veins (up to 30 mm thick) cross-cutting the albite-enriched facies of the A-type Madeira granite (∼1820 Ma), at the Pitinga mine, Presidente Figueiredo Co., Amazonas State, Brazil. Minerals in the granite are 'K-feldspar', albite, quartz, riebeckite, 'biotite', muscovite, cryolite, zircon, polylithionite, cassiterite, pyrochlore-group minerals, 'columbite', thorite, native lead, hematite, galena, fluorite, xenotime-(Y), gagarinite-(Y), fluocerite-(Ce), genthelvite–helvite, topaz, 'illite', kaolinite and 'chlorite'. The mineral occurs as massive aggregates of platy crystals up to ∼1 μm in size. Forms are not determined, but synthetic YF3 displays pinacoids, prisms and bipyramids. Colour: pale pink. Streak: white. Lustre: non-metallic. Transparent to translucent. Density (calc.) = 5.586 g/cm3 using the empirical formula. Waimirite-(Y) is biaxial, mean n = 1.54–1.56. The chemical composition is (average of 24 wavelength dispersive spectroscopy mode electron microprobe analyses, O calculated for charge balance): F 29.27, Ca 0.83, Y 37.25, La 0.19, Ce 0.30, Pr 0.15, Nd 0.65, Sm 0.74, Gd 1.86, Tb 0.78, Dy 8.06, Ho 1.85, Er 6.38, Tm 1.00, Yb 5.52, Lu 0.65, O (2.05), total (97.53) wt.%. The empirical formula (based on 1 cation) is (Y0.69Dy0.08Er0.06Yb0.05Ca0.03Gd0.02Ho0.02Nd0.01Sm0.01Tb0.01Tm0.01Lu0.01)Σ1.00[F2.54〈0.25O0.21]Σ3.00. Orthorhombic, Pnma, a = 6.386(1), b = 6.877(1), c = 4.401(1) Å, V = 193.28(7) Å3, Z = 4 (powder data). Powder X-ray diffraction (XRD) data [d in Å (I) (hkl)]: 3.707 (26) (011), 3.623 (78) (101), 3.438 (99) (020), 3.205 (100) (111), 2.894 (59) (210), 1.937 (33) (131), 1.916 (24) (301), 1.862 (27) (230). The name is for the Waimiri-Atroari Indian people of Roraima and Amazonas. A second occurrence of waimirite-(Y) is described from the hydrothermally altered quartz-rich microgranite at Jabal Tawlah, Saudi Arabia. Electron microprobe analyses gave the empirical formula (Y0.79Dy0.08Er0.05Gd0.03Ho0.02Tb0.01Tm0.01Yb0.01)Σ1.00[F2.85O0.08〈0.07]Σ3.00. The crystal structure was determined with a single crystal from Saudi Arabia. Unit-cell parameters refined from single-crystal XRD data are a = 6.38270(12), b = 6.86727(12), c = 4.39168(8) Å, V = 192.495(6) Å3, Z = 4. The refinement converged to R1 = 0.0173 and wR2 = 0.0388 for 193 independent reflections. Waimirite-(Y) is isomorphous with synthetic SmF3, HoF3 and YbF3. The Y atom forms a 9-coordinated YF9 tricapped trigonal prism in the crystal structure. The substitution of Y for Dy, as well as for other lanthanoids, causes no notable deviations in the crystallographic values, such as unit-cell parameters and interatomic distances, from those of pure YF3.
Low-crystallinity products of trace-metal precipitation in neutralized pit-lake waters without ferric and aluminous adsorbent: Geochemical modelling and mineralogical analysis
- Javier Sánchez-España, Iñaki Yusta
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- 02 January 2018, pp. 781-798
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The removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to low-crystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0–10.0. The formation of Mn3+/Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.
Rare sulfides enriched in K, Tl and Pb from the Noril'sk and Salmagorsky complexes, Russia: new data and implications
- Andrei Y. Barkov, Robert F. Martin, Louis J. Cabri
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- 02 January 2018, pp. 799-808
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New results (compositional data and reflectance values) are reported for some rare sulfides enriched in K, Tl and Pb, which are related to djerfisherite, thalfenisite, bartonite, a “Cl-bearing bartonite”, or chlorbartonite, and also for shadlunite, from the Noril'sk and Salmagorsky complexes, Russia. Our observations and comparisons with relevant data in the literature imply that: (1) bartonite is probably a S-dominant (or Cl-free) analogue of djerfisherite; and a “Cl-bearing bartonite” and chlorbartonite are probably compositional variants of the djerfisherite–bartonite series. (2) The most probable formulae of bartonite and djerfisherite are (K,Me2+)6(Fe,Cu,Ni)25–xS26(S,Cl) and (K,Me2+)6(Fe,Cu,Ni)25–xS26(Cl,S), where 0 ≤ x ≤ 5, respectively. (3) Two independent substitution mechanisms probably operate in the natural series. A coupled substitution [Me2+ + S2– ↔ K+ + Cl–] is reflected by an observed deficit in K, accompanied by the incorporation of Me2+(Pb, Fe, or Ni) in the K site. Another mechanism is inferred to be [2Fe3+ + 〈 ↔ 3Fe2+], which assumes the existence of vacancy-type defects at the Me site. Thus, the second mechanism could possibly control the existing variations of Σ(Fe, Cu, Ni) in the range of ∼21 to 25 a.p.f.u., documented in djerfisherite- and bartonite-type minerals. The minerals analysed from Noril'sk, which are free of Cl and related to bartonite and to a Tl-dominant analogue of bartonite (unnamed species), probably crystallized from microvolumes of late fluid rich in K and Tl, under conditions of relatively low oxygen fugacity in the environment. Uniform contentss of Fe and Cu, observed in coexisting phases of normal (Cl-bearing) djerfisherite and bartonite (or Cl-free analogue of djerfisherite) at Salmagorsky imply that they reached equilibrium with regard to the distribution of these elements during crystallization. These phases probably formed as a result of fluctuations in the ratios of sulfur and chlorine fugacity in a fluid at a postmagmatic hydrothermal stage.