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Stable isotope and geochemical evidence for genesis of secondary copper deposits at Girilambone, New South Wales, Australia
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- Erik B. Melchiorre
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- Journal:
- Mineralogical Magazine / Volume 86 / Issue 4 / August 2022
- Published online by Cambridge University Press:
- 28 January 2022, pp. 634-643
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The Girilambone copper deposit of New South Wales, Australia, serves as an end-member model for development of a classic oxidation-zone profile in an environment virtually free of both the effects of active tectonics and significant fluctuation in the local water table. The oxidation zone of other copper deposits may be interpreted for history of recently active tectonics, palaeoclimate, and water-table stability by comparison to the Girilambone deposit. Unlike the oxidation profiles of porphyry copper deposits of western North America, which have been overprinted by many water-table fluctuations produced by active tectonics, the Girilambone deposit appears to have little modification to the original oxidation profile. Oxidation of primary sulfides at Girilambone was an exothermic process facilitated by chemolithotrophic bacteria, recorded by malachite oxygen isotope thermometry estimates of up to 52°C, and very light malachite carbon isotope values. The bacteria generated CO2 which migrated upwards to react with copper rich meteoric fluids of the vadose zone to precipitate malachite. Unlike porphyry copper deposits of western North America which experienced recent tectonic activity, the secondary minerals (clays, iron oxides and copper carbonates) at Girilambone were not repeatedly fractured and offset during oxidation to re-establish permeability. This reduced permeability of the oxidation zone and slowed the release of CO2 from the system, producing significantly elevated partial pressure of CO2, sufficient for azurite formation to dominate. Azurite oxygen and carbon isotope values indicate formation at lower temperatures up to 32°C, and with less bacterial activity than for malachite. The sulfide-digesting bacteria at Girilambone were relatively free of seasonal swings in population, as the deposit does not have the interbanded azurite and malachite typical of episodic bacterial populations triggered by seasonal precipitation. Thus the absence of significant Cu-carbonate banding at Girilambone serves as a palaeoclimate indicator. Deeper in the Girilambone oxidation zone, native copper and cuprite dominate, whereas chalcocite formed an enrichment blanket just above and at the modern water table. Oxygen and carbon isotope values for pseudomorphs of malachite after azurite indicate that these were generated as a retrograde reaction when CO2 production from bacterial digestion of sulfides waned and temperatures in the oxidation zone were near ambient. In the post mining environment, chloride-rich groundwater seeps actively precipitate atacamite, while exposed remnants of sulfide masses form an outer rind of porous malachite. Exceptions to this oxidation zone sequence occur due to localised fluid channelisation and perched water-table lenses that generated mineralogical overprints.
Processes of metastable-mineral formation in oxidation zones and mine waste
- Juraj Majzlan
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- Journal:
- Mineralogical Magazine / Volume 84 / Issue 3 / June 2020
- Published online by Cambridge University Press:
- 18 March 2020, pp. 367-375
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Oxidation zones and mine wastes are metal-rich, near-surface environments, natural and man-made critical zones of ore deposits, respectively. They contain a number of minerals which, despite their metastability, occur consistently and in abundance. Field studies, presented as examples in this work, show that metastable minerals form not only directly from aqueous solutions, but also from more complex precursors, such as nanoparticles, gels, X-ray amorphous solids, or clusters. Initial precipitation of metastable phases and their conversion to stable phases is described by the Ostwald's step rule. Thermodynamic data show that there is a tendency, but no rule, that structurally more complex phases are also thermodynamically more stable. The Ostwald's step rule could then state that the initial metastable phases are structurally simple and easily assembled from aqueous solutions, nanoparticles, gels, disordered solids, or clusters. The structural similarity of the precursor and the forming phase is a kinetic factor favouring the crystallisation of the new phase. Calculation of saturation indices for mine drainage solutions show that they are mostly supersaturated with respect to the stable phases and the aqueous concentrations are sufficient to precipitate metastable minerals. In our fieldwork, we often encounter gelatinous substances with copper, manganese or tungsten that slowly convert to metastable oxysalt minerals. Another possibility is the crystallisation of various metastable minerals from solid, homogeneous ‘resins’ that are X-ray amorphous. Minerals typical for near-surface environments may be stabilised by their surface energy at high specific surface areas. For example, ferrihydrite is often described as a metastable phase but can be shown to be stable with respect to nanosised hematite.
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.
Leydetite, Fe(UO2)(SO4)2(H2O)11, a new uranyl sulfate mineral from Mas d’Alary, Lodève, France
- J. Plášil, A. V. Kasatkin, R. Škoda, M. Novák, A. Kallistová, M. Dušek, R. Skála, K. Fejfarová, J. Čejka, N. Meisser, H. Goethals, V. Machovič, L. Lapčák
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 4 / June 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 429-441
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Leydetite, monoclinic Fe(UO2)(SO4)2(H2O)11(IMA 2012–065), is a new supergene uranyl sulfate from Mas d'Alary, Lodève, Hérault, France. It forms yellow to greenish, tabular, transparent to translucent crystals up to 2 mm in size. Crystals have a vitreous lustre. Leydetite has a perfect cleavage on (001). The streak is yellowish white. Mohs hardness is ∼2. The mineral does not fluoresce under long- or short-wavelength UV radiation. Leydetite is colourless in transmitted light, non-pleochroic, biaxial, with α = 1.513(2), γ = 1.522(2) (further optical properties could not be measured). The measured chemical composition of leydetite, FeO 9.28, MgO 0.37, Al2O30.26, CuO 0.14, UO340.19, SO321.91, SiO20.18, H2O 27.67, total 100 wt.%, leads to the empirical formula (based on 21 O a.p.f.u.), (Fe0.93Mg0.07Al0.04Cu0.01)Σ1.05(U1.01O2)(S1.96Si0.02)Σ1.98O8(H2O)11. Leydetite is monoclinic, space group C2/c, with a = 11.3203(3), b = 7.7293(2), c = 21.8145(8) Å, β = 102.402(3)°, V = 1864.18(10) Å3, Z = 4, and Dcalc = 2.55 g cm–3. The six strongest reflections in the X-ray powder diffraction pattern are [dobs in Å (I) (hkl)]: 10.625 (100) (002), 6.277 (1) (
11), 5.321 (66) (004), 3.549 (5) (006), 2.663 (4) (008), 2.131 (2) (0 0 10). The crystal structure has been refined from single-crystal X-ray diffraction data to R1 = 0.0224 for 5211 observed reflections with [I > 3σ(I)]. Leydetite possesses a sheet structure based upon the protasite anion topology. The sheet consists of UO7 bipyramids, which share four of their equatorial vertices with SO4 tetrahedra. Each SO4 tetrahedron, in turn, shares two of its vertices with UO7 bipyramids. The remaining unshared equatorial vertex of the bipyramid is occupied by H2O, which extends hydrogen bonds within the sheet to one of a free vertex of the SO4 tetrahedron. Sheets are stacked perpendicular to the c direction. In the interlayer, Fe2+ ions and H2O groups link to the sheets on either side via a network of hydrogen bonds. Leydetite is isostructural with the synthetic compound Mg(UO2)(SO4)2(H2O)11. The name of the new mineral honours Jean Claude Leydet (born 1961), an amateur mineralogist from Brest (France), who discovered the new mineral.
Meisserite, Na5(UO2)(SO4)3(SO3OH)(H2O), a new uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah, USA
- J. Plášil, A. R. Kampf, A. V. Kasatkin, J. Marty, R. Škoda, S. Silva, J. Čejka
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- Journal:
- Mineralogical Magazine / Volume 77 / Issue 7 / October 2013
- Published online by Cambridge University Press:
- 05 July 2018, pp. 2975-2988
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Meisserite (IMA2013-039), Na5(UO2)(SO4)3(SO3OH)(H2O), is a new uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah (USA). It is named in honour of the prominent Swiss mineralogist Nicolas Meisser. The new mineral was found in a sandstone matrix and is associated with chalcanthite, copiapite, ferrinatrite, gypsum, johannite and another new Na-bearing uranyl sulfate, belakovskiite (IMA2013-075). Meisserite is a secondary mineral formed by the post-mining weathering of uraninite. The mineral is triclinic, P
, a = 5.32317(10), b = 11.5105(2), c = 13.5562(10) Å, α = 102.864(7)°, β = 97.414(7)°, γ = 91.461(6)°, V = 801.74(6) Å3, and Z = 2. Crystals are prisms elongated on [100], up to 0.3 mm long, exhibiting the forms {010} and {001}. Meisserite is pale green to yellowish green, translucent to transparent and has a very pale yellow streak. It is brittle, with fair cleavage on {100} and {001}, and uneven fracture. The Mohs hardness is estimated at 2. Meisserite is somewhat hygroscopic and easily soluble in water. The calculated density based on the empirical formula is 3.208 g/cm3. Meisserite exhibits bright yellow green fluorescence under both long- and shortwave UV radiation. The mineral is optically biaxial (–), with α = 1.514(1), β = 1.546(1), γ = 1.557(1) (measured in white light). The measured 2V is 60(2)° and the calculated 2V is 60°. Dispersion is r > v, perceptible, and the optical orientation is X ≈ a, Z ≈ c*. The mineral is pleochroic, with X (colourless) < Y (pale yellow) ≈ Z (pale greenish yellow). The empirical formula of meisserite (based on 19 O a.p.f.u.) is Na5.05(U0.94O2)(SO4)3[SO2.69(OH)1.31](H2O). The Raman spectrum is dominated by the symmetric stretching vibrations of UO22+, SO42– and also weaker O–H stretching vibrations. The eight strongest powder X-ray diffraction lines are [dobs in Å (hkl)Irel]: 13.15 (001) 81, 6.33 (0
2) 62, 5.64 (0
1,020) 52, 5.24 (100,012,
01) 100, 4.67 (101) 68, 3.849 (
1,102,022) 48, 3.614 (0
2,
3) 41, and 3.293 (
13,004) 43. The crystal structure of meisserite (R1 = 0.018 for 3306 reflections with Iobs > 3σI) is topologically unique among known structures of uranyl minerals and inorganic compounds. It contains uranyl pentagonal bipyramids linked by SO4 groups to form chains. Na+ cations bond to O atoms in the chains and to an SO3OH group and an H2>O group between the chains, thereby forming a heteropolyhedral framework.
Mineralogical and S isotopic features of the supergene profile of the Zapadno-Ozernoe massive sulphide and Au-bearing gossan deposit, South Urals
- E. V. Belogub, C. A. Novoselov, B. Spiro, B. A. Yakovleva
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- Mineralogical Magazine / Volume 67 / Issue 2 / April 2003
- Published online by Cambridge University Press:
- 05 July 2018, pp. 339-354
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The profile of the supergene zone of the Zapadno-Ozernoe massive sulphide Cu-Zn deposit differs from the classic model (Emmons, 1917) in that it includes a prominent dark sooty subzone rich in secondary sulphides. This subzone is situated above residual pyrite sands, which overlie the massive sulphide body and below quartz-baryte leached sands. It contains a diverse mineral assemblage which consists of secondary sulphides such as galena, sphalerite, metacinnabar, Se-bearing pyrite—dhzarkenite series, tiemannite, native Au, native S and native Se, and unidentified sulphosalts of Ag and Hg. The very light S isotope composition of the secondary sulphides (lowest values δ34S = —17.2‰ (VCDt) in comparison with primary pyrite ∼0‰ and baryte +18.4‰ is indicative of bacterial sulphate reduction. The overlying oxidized part of the supergene column contains minerals of the jarosite-beudantite- segnitite series. The maximum concentrations of Au, up to 150 ppm, occur in the lower part of the profile. The atypical structure, mineral assemblage and S isotope composition of the secondary sulphides in the dark layer of the supergene profile are indicative of particular geochemical conditions due to the existence of a stagnant water body that gave rise to intense bacterial activity, in turn controlled by fluctuations in the redox boundary.
Redefinition of thérèsemagnanite, NaCo4(SO4)(OH)6Cl·6H2O: new data and relationship to ‘cobaltogordaite’
- Anatoly V. Kasatkin, Jakub Plášil, Radek Škoda, Dmitriy I. Belakovskiy, Joe Marty, Nicolas Meisser, Igor V. Pekov
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- Journal:
- Mineralogical Magazine / Volume 82 / Issue 1 / February 2018
- Published online by Cambridge University Press:
- 28 February 2018, pp. 159-170
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Thérèsemagnanite was originally described from the Cap Garonne mine, Var, France. Its ideal formula was reported as (Co,Zn,Ni)6(SO4)(OH,Cl)10·8H2O; without crystal structure data, only the powder X-ray diffraction pattern was given. Revision of the holotype material revealed that thérèsemagnanite is identical to ‘cobaltogordaite’ (IMA2014-043), recently described from the Blue Lizard mine, Utah, USA. Thérèsemagnanite is thus redefined in accordance with the new data obtained for the neotype specimen from Blue Lizard (formerly the holotype specimen of ‘cobaltogordaite’) and ‘cobaltogordaite’ has been discredited by the International Mineralogical Association Commission on New Mineral Nomenclature and Classification (IMA CNMNC). Thérèsemagnanite has the ideal, end-member formula NaCo4(SO4)(OH)6Cl·6H2O. The empirical formulae of the holotype (Cap Garonne) and the neotype (Blue Lizard), both based on microprobe analyses and calculated on the basis of 17 O + Cl atoms per formula unit (with fixed 6 OH groups and 6 H2O molecules; H content is calculated by stoichiometry) are (Na0.64K0.09)Σ0.73(Co2.35Zn1.22Ni0.50)Σ4.07S1.02O3.98(OH)6Cl1.02·6H2O and Na1.01(Co1.90Zn1.37Ni0.48Cu0.15Mn0.05)Σ3.95S1.03O4.09(OH)6Cl0.91·6H2O, respectively. Thérèsemagnanite is trigonal, P
$\overline 3 $, a = 8.349(3), c = 13.031(2) Å, V = 786.6(4) Å3 and Z = 2 (neotype). The strongest powder X-ray diffraction lines are [dobs in Å (hkl) (Irel)]: 13.10 (001)(100), 6.53 (002)(8), 4.173 (110)(4), 3.517 (112)(5), 2.975 (104, 10
$\overline 4 $)(4), 2.676 (211)(5) and 2.520 (12
$\bar 2$)(5) (neotype). Thérèsemagnanite is a cobalt analogue of gordaite, NaZn4(SO4)(OH)6Cl·6H2O. These minerals represent the gordaite group, accepted by the IMA CNMNC.
Embreyite: structure determination, chemical formula and comparative crystal chemistry
- Vadim M. Kovrugin, Oleg I. Siidra, Igor V. Pekov, Nikita V. Chukanov, Dmitry A. Khanin, Atali A. Agakhanov
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- Journal:
- Mineralogical Magazine / Volume 82 / Issue 2 / April 2018
- Published online by Cambridge University Press:
- 28 February 2018, pp. 275-290
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Embreyite from the Berezovskoe, Urals, Russia, was studied by the means of powder X-ray diffraction (XRD), single-crystal XRD, infrared spectroscopy and microprobe analysis. The empirical formula of embreyite obtained on the basis of microprobe analysis is Pb1.29Cu0.07Cr0.52P0.43O4 (without taking into account the presence of H2O). An examination of single-crystal XRD frames of the tested crystals cut from embreyite intergrowths revealed split reflection spots of weak intensities, even after a long exposure time. The crystal structure of embreyite (monoclinic, C2/m, a = 9.802(16), b = 5.603(9), c = 7.649(12) Å, β = 114.85(3)o and V = 381.2(11) Å3) has been solved by direct methods and refined to R1 = 0.050 for 318 unique observed reflections. The powder XRD patterns of the holotype embreyite and the fresh material studied are close in both d values and the intensities match the pattern calculated from the structural single-crystal XRD data. The unit-cell parameters were re-calculated for the holotype sample using a new cell setting and corresponding hkl indices. The crystal structure of embreyite is based on layers formed by corner-sharing mixed chromate-phosphate tetrahedra and PbO6 distorted octahedra. The interlayer space is filled by disordered Pb2+ and Cu2+ cations. Generally, the crystal structure of embreyite can be referred to the structural type of palmierite. {Pb[(Cr,P)O4]2]} layers in embreyite are similar in topology to those in yavapaiite-type compounds. The general formula of embreyite can be represented as (Pbx
$M_y^{2 +} $□1–x–y)2{Pb[(Cr,P)O4]2}(H2O)n, where M2+ = Cu and Zn and 0.5 ≤ x + y ≤ 1, or, in the simplified form: (Pb,Cu,□)2{Pb[(Cr,P)O4]2}(H2O)n. The simplified formula of embreyite is similar in stoichiometry to vauquelinite and may explain the existence of the solid-solution series. The determination of the crystal structure of embreyite may also help to resolve the crystal chemical nature of cassedanneite. The XRD pattern of cassedanneite contains a distinct reflection with d = 13.9 Å, forbidden for the embreyite unit cell. This feature may indicate the doubling of the c unit-cell parameter of cassedanneite in comparison with embreyite. We assume that cassedanneite has structural similarity to embreyite with, presumably, a disordered distribution of Cr and V.
Nickeltsumcorite, Pb(Ni,Fe3+)2(AsO4)2 (H2O,OH)2, a new tsumcorite-group mineral from Lavrion, Greece
- Igor V. Pekov, Nikita V. Chukanov, Dmitry A. Varlamov, Dmitry I. Belakovskiy, Anna G. Turchkova, Panagiotis Voudouris, Athanassios Katerinopoulos, Andreas Magganas
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- Mineralogical Magazine / Volume 80 / Issue 2 / April 2016
- Published online by Cambridge University Press:
- 02 January 2018, pp. 337-346
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A new tsumcorite-group mineral, nickeltsumcorite, Pb(Ni,Fe3+)2(AsO4)2(H2O,OH)2, the Ni-dominant analogue of tsumcorite and cobalttsumcorite, was found in the oxidation zone of a hydrothermal orebody containing gersdorffite and galena at the Km-3 mine, Lavrion, Attikí Prefecture, Greece. It is associated with annabergite, nickellotharmeyerite, nickelaustinite, gaspéite, calcite, dolomite, aragonite, quartz, goethite, cerussite, arseniosiderite, mimetite, oxyplumboroméite and Mn oxides/hydroxides. Nickeltsumcorite occurs as open-work aggregates and interrupted crusts up to 3 mm × 5 mm in area and up to 0.2 mm thick. They typically consist of coarse radial spherulites or dense concentric nodules up to 0.15 mm in diameter. Bunches or hemispherical clusters of crude individuals and separate imperfect, elongated crystals (up to 0.02 mm long) are also observed. Nickeltsumcorite is yellow, brownish-yellow, light brown or brown, with a yellow streak and a vitreous lustre. The Mohs hardness is ∼4. The mineral is brittle; one direction of distinct cleavage is observed under the microscope. D(calc.) = 5.02 g cm–3. Nickeltsumcorite is optically biaxial (–), α = 1.82(2), β = 1.87(1), γ = 1.90(1), 2V(obs.) is large. The chemical composition (wt.%, electron-microprobe data, H2O by difference) is CaO 2.79, PbO 28.12, MgO 0.30, CoO 0.15, NiO 17.39, ZnO 0.76, Mn2O3 0.57, Fe2O3 6.83, As2O5 38.17, H2O 4.92, total 100.00. The empirical formula, calculated based on 10 O apfu, is (Pb0.76Ca0.30)∑1.06(Ni1.39Fe3+0.51Zn0.06Mn3+0.04 Mg0.04Co0.01)∑2.05As1.99O7.97[(H2O)1.25(OH)0.78]. The strongest reflections in the powder X-ray diffraction pattern [d,Å(I)(hkl)] are 4.64 (100) (1̄11), 4.47 (41)(2̄01), 3.238 (82)(1̄12), 3.008(60)(201), 2.859(41)(021), 2.545(79)(3̄12, 112), 2.545 (79)(3̄12, 112) and 2.505 (61)(220, 2̄03). The cation composition, powder Xray diffraction data and IR spectrum show that nickeltsumcorite belongs to the tsumcorite structure type. The new mineral is monoclinic, space group C2/m, a = 9.124(8), b = 6.339(3), c = 7.567(7) Å, β = 115.19(6)°, V = 396.0(7) Å3 and Z = 2. Nickeltsumcorite forms a solid-solution series with nickellotharmeyerite.
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