Hydroxylborite,Mg<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)(OH)<Subscript>3</Subscript>, a new mineral species and isomorphous series fluoborite-hydroxylborite

Hydroxylborite, a new mineral species, an analogue of fluoborite with OH > F, has been found at the Titovsky deposit (57°41′N, 125°22′E), the Chersky Range, Dogdo Basin, Sakha-Yakutia Republic, Russia. Prismatic crystals of the new mineral are dominated by the {10\(\overline 1 \)0} faces without distinct end forms and reach (1?1.5) × (0.1?0.2) mm in size. Radial aggregates of such crystals occur in the mineralized marble adjacent to the boron ore (suanite-kotoite-ludwigite). Calcite, dolomite, Mg-rich ludwigite, kotoite, szaibelyite, clinohumite, magnetite, serpentine, and chlorite are associated minerals. Hydroxylborite is transparent colorless, with a white streak and vitreous luster. The new mineral is brittle. The Mohs’ hardness is 3.5. The cleavage is imperfect on {0001}. The density measured with equilibration in heavy liquids is 2.89(1) g/cm³; the calculated density is 2.872 g/cm³. The wave numbers of the absorption bands in the IR spectrum of hydroxylborite are (cm^?1; sh is shoulder): 3668, 1233, 824, 742, 630sh, 555sh, 450sh, and 407. The new mineral is optically uniaxial, negative, ω = 1.566(1), and ε = 1.531(1). The chemical composition (electron microprobe, H₂O measured with the Penfield method, wt %) is 18.43 B₂O₃, 65.71 MgO, 10.23 F, 9.73 H₂O, 4.31-O = F₂, where the total is 99.79. The empirical formula calculated on the basis of 6 anions pfu is as follows: Mg_3.03B_0.98[(OH)_2.00F_1.00]O_3.00. Hydroxylborite is hexagonal, and the space group is P6₃/m. The unit-cell dimensions are: a = 8.912(8) Å, c = 3.112(4) Å, V = 214.05(26) ų, and Z = 2. The strongest reflections in the X-ray powder pattern [d, Å (I, %)(hkil)] are: 7.69(52)(01\(\overline 1 \)0), 4.45(82)(11\(\overline 2 \)0), 2.573(65)(03\(\overline 3 \)0), 2.422(100)(02\(\overline 2 \)1), and 2.128(60)(12\(\overline 3 \)1). The compatibility index 1 ? (K _p/K _c) is 0.038 (excellent) for the calculated density and 0.044 (good) for the measured density. The type material of hydroxylborite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow (inventory number 91968) and the Geological Museum of the All-Russia Institute of Mineral Resources, Moscow (inventory number M-1663).     

Zinclipscombite,ZnFe<Stack><Subscript>2</Subscript><Superscript>3+</Superscript></Stack>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>, a new mineral species

Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm³ measured by hydrostatic weighing and 3.727 g/cm³ calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm^?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe³⁺ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe²⁺ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al₂O₃ 4.77, Fe₂O₃ 35.14, P₂O₅ 33.86, As₂O₅ 4.05, H₂O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO₄,AsO₄)₂ is (Zn_0.76Ca_0.02)_Σ0.78(Fe _1.72 ³⁺ Al_0.36)_Σ2.08[(PO₄)_1.86(AsO₄)_0.14]_Σ2.00(OH)_{1. 80} · 0.17H₂O. The simplified formula is ZnFe ₂ ³⁺ (PO₄)₂(OH)₂. Zinclipscombite is tetragonal, space group P4₃2₁2 or P4₁2₁2; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) ų, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe²⁺Fe ₂ ³⁺ (PO₄)₂(OH)₂ (tetragonal), with Zn instead of Fe²⁺. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.     

The crystal structure of alumoklyuchevskite,K<Subscript>3</Subscript>Cu<Subscript>3</Subscript>AlO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal structure of the unstable mineral alumoklyuchevskite K₃Cu₃AlO₂(SO₄)₄ [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R ₁ = 0.131 for 2450 unique reflections with F ≥ 4σF _hkl. The structure is based on oxocentered tetrahedrons (OAlCu ₃ ⁷⁺ ) linked into chains via edges. Each chain is surrounded by SO₄ tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K₃Cu₃Fe³⁺O₂(SO₄)₄; and piypite, K₂Cu₂O(SO₄)₂.     

Geomaterials related to photovoltaics: a nanostructured Fe-bearing kuramite,Cu<Subscript>3</Subscript>SnS<Subscript>4</Subscript>

The successful synthesis of nanoparticles of Fe-bearing kuramite, (Cu,Fe)₃SnS₄, is reported in this study. Nanocrystalline powders were obtained through a mild, environmentally friendly and scalable solvothermal approach, in a single run. The sample was the object of a multidisciplinary investigation, including X-ray diffraction and absorption, scanning electron microscopy and microanalysis, electron paramagnetic resonance, diffuse reflectance and Mössbauer spectroscopy as well as SQUID magnetometry. The nanoparticles consist of pure Fe-bearing kuramite, exhibiting tetragonal structure. The valence state of the metal cations was assessed to be Cu⁺, Sn⁴⁺ and Fe³⁺. The material presents a band gap value of 1.6 eV, which is fully compatible with solar cell applications. The uptake of Fe by nanokuramite opens a compositional field where the physical properties can be tuned. We thus foster the application of Fe-bearing nanokuramite for photovoltaics and energy storage purposes.     

Batisivite,V<Subscript>8</Subscript>Ti<Subscript>6</Subscript>[Ba(Si<Subscript>2</Subscript>O)]O<Subscript>28</Subscript>, a new mineral species from the derbylite group

Batisivite has been found as an accessory mineral in the Cr-V-bearing quartz-diopside metamorphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. A new mineral was named after the major cations in its ideal formula (Ba, Ti, Si, V). Associated minerals are quartz, Cr-V-bearing diopside and tremolite; calcite; schreyerite; berdesinskiite; ankangite; V-bearing titanite; minerals of the chromite-coulsonite, eskolaite-karelianite, dravite-vanadiumdravite, and chernykhite-roscoelite series; uraninite; Cr-bearing goldmanite; albite; barite; zircon; and unnamed U-Ti-V-Cr phases. Batisivite occurs as anhedral grains up to 0.15–0.20 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black and opaque, with a black streak and resinous luster. Batisivite is white in reflected light. The microhardness (VHN) is 1220–1470 kg/mm² (load is 30 g), the mean value is 1330 kg/mm². The Mohs hardness is near 7. The calculated density is 4.62 g/cm³. The new mineral is weakly anisotropic and bireflected. The measured values of reflectance are as follows (λ, nm—R _max ^′ /R _min ^′ ): 440—17.5/17.0; 460—17.3/16.7; 480—17.1/16.5; 500—17.2/16.6; 520—17.3/16.7; 540—17.4/16.8; 560—17.5/16.8; 580—17.6/16.9; 600—17.7/17.1; 620—17.7/17.1; 640—17.8/17.1; 660—17.9/17.2; 680—18.0/17.3; 700—18.1/17.4. Batisivite is triclinic, space group P \(\overline 1\); the unit-cell dimensions are: a = 7.521(1) Å, b = 7.643(1) Å, c = 9.572(1) Å, α = 110.20°(1), β = 103.34°(1), γ = 98.28°(1), V = 487.14(7) ų, Z = 1. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)(hkl)] are: 3.09(8)(12\(\overline 2\)); 2.84, 2.85(10)(021, 120); 2.64(8)(21\(\overline 3\)); 2.12(8)(31\(\overline 3\)); 1.785(8)(32\(\overline 4\)), 1.581(10)(24\(\overline 2\)); 1.432, 1.433(10)(322, 124). The chemical composition (electron microprobe, average of 237 point analyses, wt %) is: 0.26 Nb₂O₅, 6.16 SiO₂, 31.76 TiO₂, 1.81 Al₂O₃, 8.20 VO₂, 26.27 V₂O₃, 12.29 Cr₂O₃, 1.48 Fe₂O₃, 0.08 MgO, 11.42 BaO; the total is 99.73. The VO₂/V₂O₃ ratio has been calculated. The simplified empirical formula is (V _4.8 ³⁺ Cr_2.2V _0.7 ⁴⁺ Fe_0.3)_8.0(Ti_5.4V _0.6 ⁴⁺ )_6.0[Ba(Si_1.4Al_0.5O_0.9)]O₂₈. An alternative to the title formula could be a variety (with the diorthogroup Si₂O₇) V₈Ti₆[Ba(Si₂O₇)]O₂₂. Batisivite probably pertains to the V ₈ ³⁺ Ti ₆ ⁴⁺ [Ba(Si₂O)]O₂₈-Cr ₈ ³⁺ Ti ₆ ⁴⁺ [Ba(Si₂O)]O₂₈ solid solution series. The type material of batisivite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Oxyvanite,V<Subscript>3</Subscript>O<Subscript>5</Subscript>, a new mineral species and the oxyvanite-berdesinskiite V<Subscript>2</Subscript>TiO<Subscript>5</Subscript> series from metamorphic rocks of the Slyudyanka Complex,southern Baikal region

Oxyvanite has been identified as an accessory mineral in Cr-V-bearing quartz-diopside meta- morphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. The new mineral was named after constituents of its ideal formula (oxygen and vanadium). Quartz, Cr-V-bearing tremolite and micas, calcite, clinopyroxenes of the diopside-kosmochlor-natalyite series, Cr-bearing goldmanite, eskolaite-karelianite dravite-vanadiumdravite, V-bearing titanite, ilmenite, and rutile, berdesinskiite, schreyerite, plagioclase, scapolite, barite, zircon, and unnamed U-Ti-V-Cr phases are associated minerals. Oxyvanite occurs as anhedral grains up to 0.1–0.15 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black, with black streak and resinous luster. The microhardness (VHN) is 1064–1266 kg/mm² (load 30 g), and the mean value is 1180 kg/mm². The Mohs hardness is about 7.0–7.5. The calculated density is 4.66(2) g/cm³. The color of oxyvanite is pale cream in reflected light, without internal reflections. The measured reflectance in air is as follows (λ, nm-R, %): 440-17.8; 460-18; 480-18.2; 520-18.6; 520-18.6; 540-18.8; 560-18.9; 580-19; 600-19.1; 620-19.2; 640-19.3; 660-19.4; 680-19.5; 700-19.7. Oxyvanite is monoclinic, space group C2/c; the unit-cell dimensions are a = 10.03(2), b = 5.050(1), c = 7.000(1) Å, β = 111.14(1)°, V = 330.76(5)ų, Z = 4. The strongest reflections in the X-ray powder pattern [d, Å, (I in 5-number scale)(hkl)] are 3.28 (5) (20\(\bar 2\)); 2.88 (5) (11\(\bar 2\)); 2.65, (5) (310); 2.44 (5) (112); 1.717 (5) (42\(\bar 2\)); 1.633 (5) (31\(\bar 4\)); 1.446 (4) (33\(\bar 2\)); 1.379 (5) (422). The chemical composition (electron microprobe, average of six point analyses, wt %): 14.04 TiO₂, 73.13 V₂O₃ (53.97 V₂O_3calc, 21.25 VO_2calc), 10.76 Cr₂O₃, 0.04 Fe₂O₃, 0.01 Al₂O₃, 0.02 MgO, total is 100.03. The empirical formula is (V _1.70 ³⁺ Cr_0.30)_2.0(V _0.59 ⁴⁺ Ti_0.41)_1.0O₅. Oxyvanite is the end member of the oxyvanite-berdesinskiite series with homovalent isomorphic substitution of V⁴⁺ for Ti. The type material has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Calorimetric determination of the standard enthalpy of formation of stannite,Cu<Subscript>2</Subscript>FeSnS<Subscript>4</Subscript>

The standard enthalpy of formation of stannite (Cu₂FeSnS₄) was calculated from the calorimetric measurements of the reactions of its formation from simple synthetic sulfides: Cu₂S + FeS₂ + SnS → Cu₂FeSnS₄ and ₂CuS + FeS + SnS → Cu₂FeSnS₄. Using published data for the binary sulfides, the standard enthalpy of formation of stannite from the elements was determined as ΔfH°_298.15(Cu₂FeSnS₄) =–(417.28 ± 2.28) kJ mol^–1.     

Characterisation of the antiferromagnetic transition of Cu<Subscript>2</Subscript>FeSnS<Subscript>4</Subscript>, the synthetic analogue of stannite

Magnetisation measurements were performed on the synthetic analogue of stannite, Cu₂FeSnS₄, in order to characterise the antiferromagnetic transition at low temperature, evidenced by Bernardini et al. (2000). Temperature and field dependence of the material were checked by means of static magnetisation measurements, carried out scanning the magnetic fields up to 12 T and temperatures in the range 1.4–20 K, while ac susceptibility data were collected at different frequencies ranging from 1.8 to 510 Hz. Both static and dynamic magnetisation data, performed above and below the Néel temperature, 6.1(2) K, confirm stannite to order antiferromagnetically at a long-range scale. Moreover, an increase of both the magnetic anisotropy and the exchange interaction, with respect to the Mn-analogue (Fries et al. 1997), has been observed.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Thermal expansion of new arsenate minerals,bradaczekite, NaCu<Subscript>4</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>, and urusovite,Cu(AsAlO<Subscript>5</Subscript>)

Thermal behavior of two new exhalation copper-bearing minerals, bradaczekite and urusovite, from the Great Tolbachik Fissure Eruption (1975–1976, Kamchatka Peninsula, Russia) has been studied by X-ray thermal analysis within the range 20–700°C in air. The following major values of the thermal expansion tensor have been calculated for urusovite: α₁₁ = 10, α₂₂ = α_b = 7, α₃₃ = 4, α_V = 21 × 10⁻⁶°C⁻¹, μ = c∧α₃₃ = 49° and bradaczekite: α_11aver = 23, α₂₂ = 8, α_33aver = 6 × 10⁻⁶°C⁻¹, μ(c∧α₃₃) = 73°. The sharp anisotropy of thermal deformations of these minerals, absences of phase transitions, and stability of the minerals in the selected temperature range corresponding to conditions of their formation and alteration during the posteruption period of the volcanic activity are established.     

Barioferrite BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>: A new mineral species of the magnetoplumbite group from the Haturim Formation in Israel

A new mineral barioferrite—a natural analogue of synthetic barium ferrite Ba Fe ₁₂ ³⁺ O₁₉—has been identified in the central part of a metamorphosed barite nodule in the rock of the Haturim Formation (Mottled Zone) on the southern slope of Mount Ye’elim in Israel. The mineral is associated with barite, calcite, magnetite, and maghemite and occurs as tiny platy crystals up to 3 × 15 × 15 μm and their irregular aggregates. Barioferrite is black with streaks of brown, and its luster is submetallic. Its Calculated density is 5.31 g/cm³. The mineral is brittle; cleavage is absent. IR absorption bands (cm^?1) are observed at 635 (shoulder), 582, 544, 433, and 405 (shoulder). Barioferrite is characterized by ferrimagnetic behavior. Under a microscope in reflected light, barioferrite is grayish white with brownish red internal reflections, the pleochroism is weak (from gray-white on R _o to gray-white with a brown tint on R _e), and the bireflectance is weak with distinct anisotropy. The reflectance values of R _o/R _e, % (λ, nm) are 24.51/22.80 (470), 24.17/22.25 (546), 23.65/21.68 (589), and 22.67/20.85 (650). The chemical composition (electron microprobe, wt %; the ranges are given in parentheses) is BaO 13.13 (12.5–13.8), Fe₂O₃ 86.47 (85.5–87.5), and 99.60 in total. The empirical formula is Ba_0.95Fe _12.03 ³⁺ O₁₉. Barioferrite is hexagonal with space group P6₃/mmc, a = 5.875 (3) Å, c = 23.137 (19) Å, V = 691.6 (5) ų, and Z = 2. The strongest lines of the X-ray powder diffraction pattern [d, Å, (I, 5) (hkl)] are 2.938(46) (110), 2.770(100) (107), 2.624 (84) (114, 200), 2.420(44) (203), 2.225(40) (205), and 1.627(56) (304, 2.0.11). The holotype specimen of barioferrite is deposited at the Mineralogical Museum of St. Petersburg State University; its catalogue number is 1/19436.     

Jonassonite (AuBi<Subscript>5</Subscript>S<Subscript>4</Subscript>) from the Dakripen gold deposit in Vietnam

For the first time in ore deposits of Vietnam, a mineral phase containing Au, Bi, and S as major elements was found in the gold ore of the Dakripen deposit. Pb is also present as a minor isomorphic impurity. Rare irregular or ellipsoid grains of that mineral up to 35 μm in size were identified in polished sections together with pyrite; galena; sphalerite; bismuthinite; ikunolite; native bismuth; and, occasionally, gold. All these species are related to the third stage of the ore formation. In reflected light, the mineral is bluish white, the reflectance is comparable with ikunolite and slightly higher than that of bismuthinite, and weak pleochroism and visible anisotropy are established. The mineral is opaque and brittle without internal reflections. According to 18 microprobe analyses, its average chemical composition and quantitative variations for the major elements are as follows (wt %): 14.02 (13.11–14.58) Au, 76.37 (74.93–76.91) Bi, 0.49 (0.10–1.00) Pb, 9.80 (8.87–10.07) S, and 100.68 in total. The empirical formula calculated for the average element contents—Au_0.96(Bi_4.91Pb_0.03)_4.94S_4.10—is similar to the idealized formula of jonassonite from the Nagybörzsöny deposit (Hungary)—Au(Bi,Pb)₅S₄—approved by the Commission on New Minerals and Mineral Names of the International Mineralogical Association. The typical mineral assemblage, optical properties, and chemical composition of this mineral allow us to regard it as a low-Pb variety of jonassonite. It may be assumed that the real formula of jonassonite without sporadic impurities of Pb and other elements must be AuBi₅S₄, as was stated before in the first communication of the Commission on New Minerals and Mineral Names of the International Mineralogical Association and is typical of minerals from Kazakhstan, Russia, Japan, Germany, the Czech Republic, the United States, and Australia.     

Age of tin ore from the Solnechnoe quartz-tourmaline-cassiterite deposit, the Khabarovsk krai, Russia from the results of Rb-Sr dating of quartz and adularia

The age of the main productive phase of ore formation at the large Solnechnoe tin deposit has been estimated for the first time based on the study of the Rb-Sr isotopic system of hydrothermal quartz and adularia from ore veins and metasomatic rocks. The Rb-Sr isochron age (84 ± 1 Ma) of mineralization coincides with the age of intrusive rocks pertaining to the third phase of the Silinka Complex, which control tin mineralization. The ⁸⁷Sr/⁸⁶Sr ratios of ore-forming solution and granitic rocks of the final intrusive phase are close to each other, indicating that the granitic melt was most likely one of the main sources of metals. The long and multistage formation history of the deposit could have been caused by complex geodynamic evolution of the Sikhote-Alin accretionary fold region in the Cretaceous.     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

Ivsite,Na<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>, a new mineral from volcanic exhalations of fumaroles of the Fissure Tolbachik Eruption of the 50th Anniversary of the Institute of Volcanology and Seismology,Far East Branch,Russian Academy of Sciences

Fine-granular (<0.1 mm) flattened colorless transparent crystals of ivsite form white aggregates. The empirical formula (Na_2.793Cu_0.056)_2.849HS_2.016O₈ is close to the ideal Na₃H(SO₄)₂. The structure was refined up to R = 0.040. Ivsite has a monoclinic symmetry, P2₁/c, a = 8.655(1) Å, b = 9.652(1) Å, c = 9.147(1) Å, β = 108.76(1)°, V = 723.61(1) ų, Z = 4. Na atoms occur at six- and seven-fold sites (NaO₆ and NaO₇); S atoms, in isolated SO₄ tetrahedrons; these polyhedrons form a three-dimensional framework. The diagnostic lines of powder diffraction patterns (d[Å]–I–hkl) are 4.010–53–12-1, 3.949–87–012, 3.768–100–210, 3.610–21–20-2, 3.022–22–031, 2.891–42–22-2, 2.764–49–31-1, and 2.732–70–13-1.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

Crystal chemistry of selenates with mineral-like structures. IV. Crystal structure of Zn(SeO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>, a new compound with a mixed framework of the variscite type

The crystal structure of a new compound Zn(SeO₄)(H₂O)₂ (orthorhombic, Pbca, a = 9.0411(13), b = 10.246(2), c = 10.3318(15) Å, V = 957.1(3) ų) has been solved by direct methods and refined to R ₁ = 0.033 on the basis of 1076 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure contains one independent Zn²⁺ cation coordinated by two water molecules and four oxygen atoms of selenate group. The only independent (SeO₄)^2? tetrahedral oxoanion is tetradentate, sharing its corners with four adjacent [Zn²⁺O₂(H₂O₄)]²⁺ octahedrons. The structure can be described as consisting of heteropolyhedral sheets parallel to the (001) plane and linked together into a three-dimensional network. The compound belongs to the variscite structure type and is the first structurally characterized selenate of this group.