Nickelpicromerite,K<Subscript>2</Subscript>Ni(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>•6H<Subscript>2</Subscript>O,a new picromerite-group mineral from Slyudorudnik,South Urals,Russia

A new picromerite-group mineral, nickelpicromerite, K₂Ni(SO₄)₂?·?6H₂O (IMA 2012–053), was found at the Vein #169 of the Ufaley quartz deposit, near the town of Slyudorudnik, Kyshtym District, Chelyabinsk area, South Urals, Russia. It is a supergene mineral that occurs, with gypsum and goethite, in the fractures of slightly weathered actinolite-talc schist containing partially vermiculitized biotite and partially altered sulfides: pyrrhotite, pentlandite, millerite, pyrite and marcasite. Nickelpicromerite forms equant to short prismatic or tabular crystals up to 0.07 mm in size and anhedral grains up to 0.5 mm across, their clusters or crusts up to 1 mm. Nickelpicromerite is light greenish blue. Lustre is vitreous. Mohs hardness is 2–2½. Cleavage is distinct, parallel to {10–2}. D _meas is 2.20(2), D _calc is 2.22 g cm^?3. Nickelpicromerite is optically biaxial (+), α?=?1.486(2), β?=?1.489(2), γ?=?1.494(2), 2V_meas =75(10)°, 2V_calc =76°. The chemical composition (wt.%, electron-microprobe data) is: K₂O 20.93, MgO 0.38, FeO 0.07, NiO 16.76, SO₃ 37.20, H₂O (calc.) 24.66, total 100.00. The empirical formula, calculated based on 14 O, is: K_1.93Mg_0.04Ni_0.98S_2.02O_8.05(H₂O)_5.95. Nickelpicromerite is monoclinic, P2₁/c, a?=?6.1310(7), b?=?12.1863(14), c?=?9.0076(10) Å, β?=?105.045(2)°, V?=?649.9(1) ų, Z?=?2. Eight strongest reflections of the powder XRD pattern are [d,Å-I(hkl)]: 5.386–34(110); 4.312–46(002); 4.240–33(120); 4.085–100(012, 10–2); 3.685–85(031), 3.041–45(040, 112), 2.808–31(013, 20–2, 122), 2.368–34(13–3, 21–3, 033). Nickelpicromerite (single-crystal X-ray data, R?=?0.028) is isostructural to other picromerite-group minerals and synthetic Tutton’s salts. Its crystal structure consists of [Ni(H₂O)₆]²⁺ octahedra linked to (SO₄)^2? tetrahedra via hydrogen bonds. K⁺ cations are coordinated by eight anions. Nickelpicromerite is the product of alteration of primary sulfide minerals and the reaction of the acid Ni-sulfate solutions with biotite.     

Mangazeite,Al<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)(OH)<Subscript>4</Subscript> · 3H<Subscript>2</Subscript>O,a new mineral species

Mangazeite, a new mineral species, has been found at the Mangazeya silver deposit (300 km east of the Lena River, 65°43′40″ N and 130°20′ E) in eastern Yakutia (Sakha Republic, Siberia, Russia). The new mineral was described from fractured, sericitized, and pyritized granodiorite adjacent to a quartz-arsenopyrite vein. Associated minerals are gypsum and chlorite. The new mineral occurs as radial fibrous segregations of thin lamellar crystals. The size of the fibers does not exceed 40 μm in length and 1 μm across. The mineral is white, with a white streak and a vitreous luster. Mangazeite is transparent in isolated grains. No fluorescence is observed. The Mohs hardness is 1–2. The calculated density is 2.15 g/cm³. The new mineral is biaxial; its optical character was not determined; α = 1.525(9), β was not measured, and γ = 1.545(9). The average chemical composition is as follows (wt %): Al₂O₃ 36.28, SO₃ 28.81, H₂O⁺ 34.35, total 99.44, H₂O^? 9.27. The H₂O^? content was neither included in the total nor used in formula calculation. The empirical formula is Al_1.99(SO₄)_1.01(OH)_3.94 · 3.37H₂O. The simplified formula is Al₂(SO₄)(OH)₄ · 3H₂O. The theoretical chemical composition calculated from this formula is (wt %) Al₂O₃ 37.47, SO₃ 29.42, H₂O 33.11, total 100.00. The new mineral is triclinic; the unit cell parameters refined from X-ray powder diffraction data are a = 8.286(5), b = 9.385(5), c = 11.35(1) Å, α = 96.1(1), β = 98.9(1), γ = 96.6(1)°, and Z = 4. The strongest lines in the X-ray powder diffraction pattern (d(I, %)) are 8.14(19), 7.59(49), 7.16(46), 4.258(100), 4.060(48), and 3.912(43). Mangazeite is supergene in origin and crystallized in a favorable aluminosilicate environment in the presence of sulfate ion due to pyrite oxidation.     

Measurements and calculations of solid-liquid equilibria in the ternary systems NaBr–Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O and KBr–K<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O at 348 K

According to the compositions of the underground brine resources in the west of Sichuan Basin, solubilities of the ternary systems NaBr–Na₂SO₄–H₂O and KBr–K₂SO₄–H₂O were investigated by isothermal method at 348 K. The equilibrium solid phases, solubilities of salts, and densities of the solutions were determined. On the basis of the experimental data, the phase diagrams and the density-composition diagrams were plotted. In the two ternary systems, the phase diagrams consist of two univariant curves, one invariant point and two crystallization fields. Neither solid solution nor double salts were found. The equilibrium solid phases in the ternary system NaBr–Na₂SO₄–H₂O are NaBr and Na₂SO₄, and those in the ternary system KBr–K₂SO₄–H₂O are KBr and K₂SO₄. Using the solubilities data of the two ternary subsystems at 348 K, mixing ion-interaction parameters of Pitzer’s equation θxxx, Ψxxx and Ψxxx were fitted by multiple linear regression method. Based on the chemical model of Pitzer’s electrolyte solution theory, the solubilities of phase equilibria in the two ternary systems NaBr–Na₂SO₄–H₂O and KBr–K₂SO₄–H₂O were calculated with corresponding parameters. The calculation diagrams were plotted. The results showed that the calculated values have a good agreement with experimental data.     

Nickeltalmessite,Ca<Subscript>2</Subscript>Ni(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O,a new mineral species of the fairfieldite group,Bou Azzer,Morocco

Nickeltalmessite, Ca₂Ni(AsO₄)₂ · 2H₂O, a new mineral species of the fairfieldite group, has been found in association with annabergite, nickelaustinite, pecoraite, calcite, and a mineral of the chromite-manganochromite series from the dump of the Aït Ahmane Mine, Bou Azzer ore district, Morocco. The new mineral occurs as spheroidal aggregates consisting of split crystals up to 10 × 10 × 20 μm in size. Nickeltalmessite is apple green, with white streak and vitreous luster. The density measured by the volumetric method is 3.72(3) g/cm³; calculated density is 3.74 g/cm³. The new mineral is colorless under a microscope, biaxial, positive: α = 1.715(3), β = 1.720(5), γ = 1.753(3), 2V _meas = 80(10)°, 2V _calc = 60.4. Dispersion is not observed. The infrared spectrum is given. As a result of heating of the mineral in vacuum from 24° up to 500°C, weight loss was 8.03 wt %. The chemical composition (electron microprobe, wt %) is as follows: 25.92 CaO, 1.23 MgO, 1.08 CoO, 13.01 NiO, 52.09 As₂O₅; 7.8 H₂O (determined by the Penfield method); the total is 101.13. The empirical formula calculated on the basis of two AsO₄ groups is Ca_2.04(Ni_0.77Mg_0.13Co_0.06)_Σ0.96 (AsO₄)_2.00 · 1.91H₂O. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are: 5.05 (27) (001) (100), 3.57 (43) (011), 3.358 (58) (110), 3.202 (100) (020), 3.099 (64) (0\(\bar 2\)1), 2.813 (60), (\(\bar 1\)21), 2.772 (68) (2\(\bar 1\)0), 1.714 (39) (\(\bar 3\)31). The unit-cell dimensions of the triclinic lattice (space group P1 or P) determined from the X-ray powder data are: a = 5.858(7), b = 7.082(12), c = 5.567(6) Å, α = 97.20(4), β = 109.11(5), γ = 109.78(5)°, V = 198.04 ų, Z = 1. The mineral name emphasizes its chemical composition as a Ni-dominant analogue of talmessite. The type material of nickeltalmessite is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, registration number 3750/1.     

Thermal expansion of hydrated six-coordinate silicon in thaumasite,Ca<Subscript>3</Subscript>Si(OH)<Subscript>6</Subscript>(CO<Subscript>3</Subscript>)(SO<Subscript>4</Subscript>)·12H<Subscript>2</Subscript>O

Thaumasite, Ca₃Si(OH)₆(CO₃)(SO₄)12H₂O, occurs as a low-temperature secondary alteration phase in mafic igneous and metamorphic rocks, and is recognized as a product and indicator of sulfate attack in Portland cement. It is also the only mineral known to contain silicon in six-coordination with hydroxyl (OH)^? that is stable at ambient P–T conditions. Thermal expansion of the various components of this unusual structure has been determined from single-crystal X-ray structure refinements of natural thaumasite at 130 and 298 K. No phase transitions were observed over this temperature range. Cell parameters at room temperature are: a= 11.0538(6) Å, c=10.4111(8) Å and V=1101.67(10) ų, and were measured at intervals of about 50 K between 130 and 298 K, resulting in mean axial and volumetric coefficients of thermal expansion (×10^?5K^?1); α _a =1.7(1), α _c =2.1(2), and α _V =5.6(2). Although the unit cell and ^VIIICaO₈ polyhedra show significant positive thermal expansion over this temperature range, the silicate octahedron, sulfate tetrahedron, and carbonate group show zero or negative thermal expansion, with α _V (^VISiO₆) = ?0.6 ± 1.1, α _V (^IVSO₄)=?5.8 ± 1.4, and α _R (C–O)= 0.0 ± 1.8 (×10^?5 K^?1). Most of the thermal expansion is accommodated by lengthening of the R(O...O) hydrogen bond distances by on average 5σ, although the hydrogen bonds involving hydroxyl sites on ^VISi expand twice as much as those on molecular water, causing the [Ca₃Si(OH)₆(H₂O)₁₂]⁴⁺ columns to expand in diameter more than they move apart over this temperature range. The average Si–OH bond length of the six-coordinated Si atom 〈R(^VISi–OH)〉 in thaumasite is 1.783(1) Å, being about 0.02 Å (?20σ) shorter than ^VISi–OH in the dense hydrous magnesium silicate, phase D, MgSi₂H₂O₆.     

Attikaite,Ca<Subscript>3</Subscript>Cu<Subscript>2</Subscript>Al<Subscript>2</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>4</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O,a new mineral species

Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm³ (measured in heavy liquids) and 3.356 g/cm³ (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm^?1; sh is shoulder; w is a weak band): 3525sh, 3425, 3180, 1642, 1120w, 1070w, 1035w, 900sh, 874, 833, 820, 690w, 645w, 600sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) (X = c) 2V _means = 10(8)°, and 2V _calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al₂O₃, 0.89 P₂O₅, 45.45 As₂O₅, 1.39 SO₃, and H₂O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H₂O)₂₂ is: Ca_2.94Cu _1.93 ²⁺ Al_1.97Mg_0.04Fe _0.02 ²⁺ [(As_3.74S_0.16P_0.12)_Σ4.02O_16.08](OH)_3.87 · 2.05H₂ O. The simplified formula is Ca₃Cu₂Al₂(AsO₄)₄(OH)₄ · 2H₂O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) ų, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128–140°, the H₂O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H₂O molecules per formula; and parameter c decreases from 22.78 to 18.77 Å. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)((hkl)] are: 22.8(100)(001), 11.36(60)(002), 5.01(90)(200), 3.38(5)(123, 205), 2.780(70)(026), 2.682(30)(126), 2.503(50)(400), 2.292(20)(404). The type material of attikaite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. The registration number is 3435/1.     

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.     

Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

High-pressure X-ray diffraction and Raman spectroscopy of CaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-type β-CaCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

In situ high-pressure synchrotron X-ray diffraction and Raman spectroscopic studies of orthorhombic CaFe₂O₄-type β-CaCr₂O₄ chromite were carried out up to 16.2 and 32.0 GPa at room temperature using multi-anvil apparatus and diamond anvil cell, respectively. No phase transition was observed in this study. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a zero-pressure volume of V ₀ = 286.8(1) ų, an isothermal bulk modulus of K ₀ = 183(5) GPa and the first pressure derivative of isothermal bulk modulus K ₀′ = 4.1(8). Analyses of axial compressibilities show anisotropic elasticity for β-CaCr₂O₄ since the a-axis is more compressible than the b- and c-axis. Based on the obtained and previous results, the compressibility of several CaFe₂O₄-type phases was compared. The high-pressure Raman spectra of β-CaCr₂O₄ were analyzed to determine the pressure dependences and mode Grüneisen parameters of Raman-active bands. The thermal Grüneisen parameter of β-CaCr₂O₄ is determined to be 0.93(2), which is smaller than those of CaFe₂O₄-type CaAl₂O₄ and MgAl₂O₄.     

Dachiardite-K, (K<Subscript>2</Subscript>Ca)(Al<Subscript>4</Subscript>Si<Subscript>20</Subscript>O<Subscript>48</Subscript>) · 13H<Subscript>2</Subscript>O,a new zeolite from Eastern Rhodopes,Bulgaria

Dachiardite-K (IMA No. 2015-041), a new zeolite, is a K-dominant member of the dachiardite series with the idealized formula (К₂Са)(Al₄Si₂₀O₄₈) · 13H₂О. It occurs in the walls of opal–chalcedony veinlets cutting hydrothermally altered effusive rocks of the Zvezdel paleovolcanic complex near the village of Austa, Momchilgrad Municipality, Eastern Rhodopes, Bulgaria. Chalcedony, opal, dachiardite-Ca, dachiardite-Na, ferrierite-Mg, ferrierite-K, clinoptilolite-Ca, clinoptilolite-K, mordenite, smectite, celadonite, calcite, and barite are associated minerals. The mineral forms radiated aggregates up to 8 mm in diameter consisting of split acicular individuals. Dachiardite-K is white to colorless. Perfect cleavage is observed on (100). D _meas = 2.18(2), D _calc = 2.169 g/cm³. The IR spectrum is given. Dachiardite-K is biaxial (+), α = 1.477 (calc), β = 1.478(2), γ = 1.481(2), 2V _meas = 65(10)°. The chemical composition (electron microprobe, mean of six point analyses, H₂O determined by gravimetric method) is as follows, wt %: 4.51 K₂O, 3.27 CaO, 0.41 BaO, 10.36 A1₂O₃, 67.90 SiO₂, 13.2 H₂O, total is 99.65. The empirical formula is H_26.23K_1.71Ca_1.04Ba_0.05Al_3.64Si_20.24O₆₁. The strongest reflections in the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 9.76 (24) (001), 8.85 (58) (200), 4.870 (59) (002), 3.807 (16) (202), 3.768 (20) (112, 020), 3.457 (100) (220), 2.966 (17) (602). Dachiardite-K is monoclinic, space gr. C2/m, Cm or C2; the unit cell parameters refined from the powder X-ray diffraction data are: a = 18.670(8), b = 7.511(3), c = 10.231(4) Å, β = 107.79(3)°, V= 1366(1) ų, Z = 1. The type specimen has been deposited in the Earth and Man National Museum, Sofia, Bulgaria, with the registration number 23927.     

Tinnunculite,C<Subscript>5</Subscript>H<Subscript>4</Subscript>N<Subscript>4</Subscript>O<Subscript>3</Subscript> · 2H<Subscript>2</Subscript>O: Occurrences on the Kola Peninsula and Redefinition and Validation as a Mineral Species

Based on a study of samples found in the Khibiny (Mt. Rasvumchorr: the holotype) and Lovozero (Mts Alluaiv and Vavnbed) alkaline complexes on the Kola Peninsula, Russia, tinnunculite was approved by the IMA Commission on New Minerals, Nomenclature, and Classification as a valid mineral species (IMA no. 2015-02la) and, taking into account a revisory examination of the original material from burnt dumps of coal mines in the southern Urals, it was redefined as crystalline uric acid dihydrate (UAD), C₅H₄N₄O₃ · 2H₂O. Tinnunculite is poultry manure mineralized in biogeochemical systems, which could be defined as “guano microdeposits.” The mineral occurs as prismatic or tabular crystals up to 0.01 × 0.1 × 0.2 mm in size and clusters of them, as well as crystalline or microglobular crusts. Tinnunculite is transparent or translucent, colorless, white, yellowish, reddish or pale lilac. Crystals show vitreous luster. The mineral is soft and brittle, with a distinct (010) cleavage. D_calc = 1.68 g/cm³ (holotype). Tinnunculite is optically biaxial (–), α = 1.503(3), β = 1.712(3), γ = 1.74(1), 2V_obs = 40(10)°. The IR spectrum is given. The chemical composition of the holotype sample (electron microprobe data, content of H is calculated by UAD stoichiometry) is as follows, wt %: 37.5 О, 28.4 С, 27.0 N, 3.8 H_calc, total 96.7. The empirical formula calculated on the basis of (C + N+ O) = 14 apfu is: C_4.99H₈N_4.07O_4.94. Tinnunculite is monoclinic, space group (by analogy with synthetic UAD) P2₁/c. The unit cell parameters of the holotype sample (single crystal XRD data) are a = 7.37(4), b = 6.326(16), c = 17.59(4) Å, β = 90(1)°, V = 820(5) ų, Z = 4. The strongest reflections in the XRD pattern (d, Å–I[hkl]) are 8.82–84[002], 5.97–15[011], 5.63–24[102?, 102], 4.22–22[112], 3.24–27[114?,114], 3.18–100[210], 3.12–44[211?, 211], 2.576–14[024].     

Single-crystal X-ray diffraction study of cation distribution in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel solid solution

Synthesis experiments in the system MgAl₂O₄–MgFe₂O₄ [MgAl_2–xFe_xO₄ (0 x 2)] were carried out using a PbF₂ flux. The crystalline products synthesized in the compositional range of 0.6 <x 1.2 consisted of two spinel phases, whereas those synthesized in the compositional ranges of 0.0 x 0.6 and 1.2 < x 2.0 crystallized as single spinel phases. Structure refinements of the spinel single crystals, which grew in the ranges of 0.0 x 0.6 and 1.2 < x 2.0, show that the degree of randomness of cation distribution between A and B sites increases as x approaches the two-phase region. This means that the degree of the size mismatch among Mg²⁺, Fe³⁺ and Al³⁺occupying each equivalent mixing site increases as x approaches the two-phase region. Consequently, if the coexistence of two spinels observed in the intermediate compositions reveals the existence of a miscibility gap at low temperatures, this increase in the degree of the size mismatch among the three cations is suggested as a factor of energetic destabilization to form the miscibility gap.     

Characterization of synthetic hedenbergite (CaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)–petedunnite (CaZnSi<Subscript>2</Subscript>O<Subscript>6</Subscript>) solid solution series by X-ray powder diffraction and <Superscript>57</Superscript>Fe Mössbauer spectroscopy

Clinopyroxenes along the solid solution series hedenbergite (CaFeSi₂O₆)–petedunnite (CaZnSi₂O₆) were synthesized under hydrothermal conditions and different oxygen fugacities at temperatures of 700 to 1200 °C and pressures of 0.2 to 2.5 GPa. Properties were determined by means of X-ray diffraction, electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy at 298 K. Unit-cell parameters display a linear dependency with changing composition. Parameters a₀ and b₀ exhibit a linear decrease with increasing Zn content while the monoclinic angle increases linearly. Parameter c₀ is not affected by composition and remains constant at a value of 5.248 Å. The molar volume can be described according to the equation V_mol (ccm mol^–1)=33.963(16)–0.544(31)*Zn pfu. The isomer shifts of ferrous iron on the octahedral M1 site in hedenbergite are not affected by composition along the hedenbergite–petedunnite solid solution series and remain constant at an average value of 1.18 mm s^–1. Quadrupole splittings of Fe²⁺ on the M1 are, however, strongly affected by composition, and they decrease linearly with increasing petedunnite component in hedenbergite, ranging from 2.25 mm s^–1 for pure hedenbergite end member to 1.99 mm s^–1 for a solid solution containing 84 mole% petedunnite. The half-widths of intermediate solid solutions vary between 0.26 and 0.33 mm s^–1, indicating, in accordance with the microprobe analyses and X-ray diffraction, that samples are homogeneous and well-crystallized. The data from this study demonstrate that the crystallinity of hedenbergitic clinopyroxenes can be improved by using oxide mixtures as starting materials. Crystal sizes for intermediate compositions range up to 70 m, suitable for standard single-crystal X-ray analysis.This paper is dedicated to Prof. Dr. Georg Amthauer, Salzburg, on occasion of his 60th birthday     

Avdoninite: New data,crystal structure and refined formula K<Subscript>2</Subscript>Cu<Subscript>5</Subscript>Cl<Subscript>8</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O

The paper reports new findings of avdoninite from deposits of active fumaroles in the Second Scoria Cone at the Northern Breach of the Great Fissure Tolbachik Eruption, Tolbachik Volcano, Kamchatka Peninsula, Russia. The crystal structure of the mineral has been determined for the first time, which has allowed reliable determination of its space group and unit cell dimensions, refinement of its formula K₂Cu₅-Cl₈(OH)₄ · 2H₂O, and correct indexing of its X-ray powder diffraction pattern. Avdoninite is monoclinic, space group P2₁/c, a = 11.592(2), b = 6.5509(11), c = 11.745(2) Å, β = 91.104(6)°, V = 891.8(3) ų, Z = 2. The crystal structure of this mineral has been determined on a single crystal R ₁ [F > 4σ (F)] = 0.063. It is based on sheets of copper–oxo-chloride complexes [Cu₅Cl₈(OH)₄]^2– parallel to (100). The K⁺ cation and H₂O molecules are interlayers.     

The thermal expansion and crystal structure of mirabilite (Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·10D<Subscript>2</Subscript>O) from 4.2 to 300 K,determined by time-of-flight neutron powder diffraction

We have collected high resolution neutron powder diffraction patterns from Na₂SO₄·10D₂O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P2₁/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å³ at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å³ at 300 K. Structures were refined to R _P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10^?7 T ³ + 0.00047(2) T² ? 0.027(2) T + 1437.0(1) Å³ (R ² = 99.98%). The coefficient of volume thermal expansion, α _V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α _V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.     

Tatarinovite Са<Subscript>3</Subscript>Al(SO<Subscript>4</Subscript>)[В(ОH)<Subscript>4</Subscript>](ОH)<Subscript>6</Subscript> · 12H<Subscript>2</Subscript>O,a new ettringite-group mineral from the Bazhenovskoe deposit,Middle Urals,Russia, and its crystal structure

A new mineral, tatarinovite, ideally Са₃Аl(SO₄)[В(ОН)₄](ОН)₆ · 12Н₂O, has been found in cavities of rhodingites at the Bazhenovskoe chrysotile asbestos deposit, Middle Urals, Russia. It occurs (1) colorless, with vitreous luster, bipyramidal crystals up to 1 mm across in cavities within massive diopside, in association with xonotlite, clinochlore, pectolite and calcite, and (2) as white granular aggregates up to 5 mm in size on grossular with pectolite, diopside, calcite, and xonotlite. The Mohs hardness is 3; perfect cleavage on (100) is observed. D _meas = 1.79(1), D _calc = 1.777 g/cm³. Tatarinovite is optically uniaxial (+), ω = 1.475(2), ε = 1.496(2). The IR spectrum contains characteristic bands of SO₄ ^2?, CO₃ ^2?, B(OH)₄ ^?, B(OH)₃, Al(OH)₆ ^3-, Si(OH)₆ ^2-, OH^–, and H₂O. The chemical composition of tatarinovite (wt %; ICP-AES; H₂O was determined by the Alimarin method; CO₂ was determined by selective sorption on askarite) is as follows: 27.40 CaO, 4.06 B₂O₃, 6.34 A1₂O₃, 0.03 Fe₂O₃, 2.43 SiO₂, 8.48 SO₃, 4.2 CO₂, 46.1 H₂O, total is 99.04. The empirical formula (calculated on the basis of 3Ca apfu) is H_31.41Ca_3.00(Al_0.76Si_0.25)_Σ1.01 · (B_0.72S_0.65C_0.59)Σ_1.96O_24.55. Tatarinovite is hexagonal, space gr. P6₃, a = 11.1110(4) Å, c = 10.6294(6) Å, V = 1136.44(9) A³, Z = 2. Its crystal chemical formula is Са₃(Аl_0.70Si_0.30) · {[SO₄]_0.34[В(ОН)₄]_0.33[СO₃]0.₂₄}{[SO₄]_0.30[В(ОН)₄]_0.34[СО₃]_0.30[В(ОН)₃]_0.06}(ОН_5·73О_0.27) · 12Н₂O. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are 9.63 (100) (100), 5.556 (30) (110), 4.654 (14) (102), 3.841 (21) (112), 3.441 (12) (211), 2.746 (10) (302), 2.538 (12) (213). Tatarinovite was named in memory of the Russian geologist and petrologist Pavel Mikhailovich Tatarinov (1895–1976), a well-known specialist in chrysotile asbestos deposits. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Kamarizaite,Fe<Stack><Subscript>3</Subscript><Superscript>3+</Superscript></Stack>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>3</Subscript> · 3H<Subscript>2</Subscript>O,a new mineral species,arsenate analogue of tinticite

Kamarizaite, a new mineral species, has been identified in the dump of the Kamariza Mine, Lavrion mining district, Attica Region, Greece, in association with goethite, scorodite, and jarosite. It was named after type locality. Kamarizaite occurs as fine-grained monomineralic aggregates (up to 3 cm across) composed of platy crystals up to 1 μm in size and submicron kidney-shaped segregations. The new mineral is yellow to beige, with light yellow streak. The Mohs hardness is about 3. No cleavage is observed. The density measured by hydrostatic weighing is 3.16(1) g/cm³, and the calculated density is 3.12 g/cm³. The wavenumbers of absorption bands in the IR spectrum of kamarizaite are (cm^?1; s is strong band, w is weak band): 3552, 3315s, 3115, 1650w, 1620w, 1089, 911s, 888s, 870, 835s, 808s, 614w, 540, 500, 478, 429. According to TG and IR data, complete dehydration and dehydroxylation in vacuum (with a weight loss of 15.3(1)%) occurs in the temperature range 110–420°C. Mössbauer data indicate that all iron in kamarizaite is octahedrally coordinated Fe³⁺. Kamarizaite is optically biaxial, positive: n _min = 1.825, n _max = 1.835, n _mean = 1.83(1) (for a fine-grained aggregate). The chemical composition of kamarizaite (electron microprobe, average of four point analyses) is as follows, wt %: 0.35 CaO, 41.78 Fe₂O₃, 39.89 As₂O₅, 1.49 SO₃, 15.3 H₂O (from TG data); the total is 98.81. The empirical formula calculated on the basis of (AsO₄,SO₄)₂ is Ca_0.03Fe _2.86 ³⁺ (AsO₄)_1.90(SO₄)_0.10(OH)_2.74 · 3.27H₂O. The idealized formula is Fe ₃ ³⁺ (AsO₄)₂(OH)₃ · 3H₂O. Kamarizaite is an arsenate analogue of orthorhombic tinticite, space group Pccm, Pcc2, Pcmm, Pcm2₁, or Pc2m; a = 21.32(1), b = 13.666(6), c =15.80(1) Å, V= 4603.29(5) ų, Z= 16. The strongest reflections of the X-ray powder diffraction pattern [\(\bar d\), Å (I, %) (hkl)] are: 6.61 (37) (112, 120), 5.85 (52) (311), 3.947 (100) (004, 032, 511), 3.396 (37) (133, 431), 3.332 (60) (314), 3.085 (58) (621, 414, 324). The type material of kamarizaite is deposited in the Mineralogical Collection of Technische Universität Bergakademie Freiberg, Germany, inventory number 82199.     

Middendorfite,K<Subscript>3</Subscript>Na<Subscript>2</Subscript>Mn<Subscript>5</Subscript>Si<Subscript>12</Subscript>(O,OH)<Subscript>36</Subscript> · 2H<Subscript>2</Subscript>O,a new mineral species from the Khibiny pluton,Kola Peninsula

Middendorfite, a new mineral species, has been found in a hydrothermal assemblage in Hilairite hyperperalkaline pegmatite at the Kirovsky Mine, Mount Kukisvumchorr apatite deposit, Khibiny alkaline pluton, Kola Peninsula, Russia. Microcline, sodalite, cancrisilite, aegirine, calcite, natrolite, fluorite, narsarsukite, labuntsovite-Mn, mangan-neptunite, and donnayite are associated minerals. Middendorfite occurs as rhombshaped lamellar and tabular crystals up to 0.1 × 0.2 × 0.4 mm in size, which are combined in worm-and fanlike segregations up to 1 mm in size. The color is dark to bright orange, with a yellowish streak and vitreous luster. The mineral is transparent. The cleavage (001) is perfect, micalike; the fracture is scaly; flakes are flexible but not elastic. The Mohs hardness is 3 to 3.5. Density is 2.60 g/cm³ (meas.) and 2.65 g/cm³ (calc.). Middendorfite is biaxial (?), α = 1.534, β = 1.562, and γ = 1.563; 2V (meas.) = 10°. The mineral is pleochroic strongly from yellowish to colorless on X through brown on Y and to deep brown on Z. Optical orientation: X = c. The chemical composition (electron microprobe, H₂O determined with Penfield method) is as follows (wt %): 4.55 Na₂O, 10.16 K₂O, 0.11 CaO, 0.18 MgO, 24.88 MnO, 0.68 FeO, 0.15 ZnO, 0.20 Al₂O₃, 50.87 SiO₂, 0.17 TiO₂, 0.23 F, 7.73 H₂O; ?O=F₂?0.10, total is 99.81. The empirical formula calculated on the basis of (Si,Al)₁₂(O,OH,F)₃₆ is K_3.04(Na_2.07Ca_0.03)_Σ2.10(Mn_4.95Fe_0.13Mg_0.06Ti_0.03Zn_0.03)_Σ5.20(Si_11.94Al_0.06)_Σ12O_27.57(OH)_8.26F_0.17 · 1.92H₂O. The simplified formula is K₃Na₂Mn₅Si₁₂(O,OH)₃₆ · 2H₂O. Middenforite is monoclinic, space group: P2₁/m or P2₁. The unit cell dimensions are a = 12.55, b = 5.721, c = 26.86 Å; β = 114.04°, V = 1761 ų, Z = 2. The strongest lines in the X-ray powder pattern [d, Å, (I)(hkl)] are: 12.28(100)(002), 4.31(81)(11\(\overline 4 \)), 3.555(62)(301, 212), 3.063(52)(008, 31\(\overline 6 \)), 2.840(90)(312, 021, 30\(\overline 9 \)), 2.634(88)(21\(\overline 9 \), 1.0.\(\overline 1 \)0, 12\(\overline 4 \)), 2.366(76)(22\(\overline 6 \), 3.1.\(\overline 1 \)0, 32\(\overline 3 \)), 2.109(54)(42–33, 42–44, 51\(\overline 9 \), 414), 1.669(64)(2.2.\(\overline 1 \)3, 3.2.\(\overline 1 \)3, 62\(\overline 3 \), 6.1.\(\overline 1 \)3), 1.614(56)(5.0.\(\overline 1 \)6, 137, 333, 71\(\overline 1 \)). The infrared spectrum is given. Middendorfite is a phyllosilicate related to bannisterite, parsenttensite, and the minerals of the ganophyllite and stilpnomelane groups. The new mineral is named in memory of A.F. von Middendorff (1815–1894), an outstanding scientist, who carried out the first mineralogical investigations in the Khibiny pluton. The type material of middenforite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

X-ray single-crystal and Raman study of (Na<Subscript>0.86</Subscript>Mg<Subscript>0.14</Subscript>)(Mg<Subscript>0.57</Subscript>Ti<Subscript>0.43</Subscript>)Si<Subscript>2</Subscript>O<Subscript>6</Subscript>, a new pyroxene synthesized at 7 GPa and 1700 °C

A new pyroxene with formula (Na_0.86Mg_0.14)(Mg_0.57Ti_0.43)Si₂O₆, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) ų. The coexistence of Mg and Ti⁴⁺ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg₂Si₂O₆ (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.