Crystal chemistry of selenates with mineral-like structures: V. Crystal structures of (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 and (H3O)2[(UO2)(SeO4)2(H2O)](H2O), new compounds with rhomboclase and goldichite topology

The crystal structures of two new compounds (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O)₂ (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) ų) and (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O) (2, monoclinic, P2₁/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) ų) have been solved by direct methods and refined to R ₁ = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO₂)(SeO₄)₂]^2? formed by cornershared [(UO₂)O₄(H₂O)] bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO₂)(SeO₄)₂(H₂O)]^2? layers are linked by hydrogen bonds via interlayer groups H₂O and H₃O⁺. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H₂O₂)⁺[Fe(SO₄)₂(H₂O)₂] and goldichite K[Fe(SO₄)₂(H₂O)₂](H₂O)₂, respectively.     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2⋅17-18H2O

Albrechtschraufite, MgCa₄F₂[UO₂(CO₃)₃]₂?17-18H₂O, triclinic, space group Pī, a?=?13.569(2), b?=?13.419(2), c?=?11.622(2) Å, α?=?115.82(1), β?=?107.61(1), γ?=?92.84(1)° (structural unit cell, not reduced), V?=?1774.6(5) ų, Z?=?2, D _c?=?2.69 g/cm³ (for 17.5 H₂O), is a mineral that was found in small amounts with schröckingerite, NaCa₃F[UO₂(CO₃)₃](SO₄)?10H₂O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca₂[UO₂(CO₃)₃]??~?11H₂O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX?=?1.511(2), nY?=?1.550(2), nZ?=?1.566(2), 2?V?=?65(1)° (λ?=?589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO₂ and H₂O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1?=?0.0206 and wR2?=?0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO₂(CO₃)₃]^4? anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF₂(O_carbonate)₃(H₂O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO₆, CaF₂O₂(H₂O)₄, CaFO₃(H₂O)₄ and CaO₂(H₂O)₆ coordination polyhedra. The crystal structure is built up from MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers parallel to (001) which are linked by Ca[UO₂(CO₃)₃]?5H₂O moieties into a framework of the composition MgCa₄F₂[UO₂(CO₃)₃]?13H₂O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a total water content of 17-18H₂O per formula unit. The MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO₂(CO₃)₃]₄Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.     

Hydration vs. oxidation: Modelling implications for Fe–Ti oxide crystallisation in mafic intrusions, with specific reference to the Panzhihua intrusion, SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion:（1） low-Ti,high CaO and low H₂O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H₂O（>1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ + 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O₂） and H₂O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H₂O contents（0.5-1 wt.%） but at the lower end of TiO₂ content for typical high-Ti basalts（2.5 wt.%TiO₂）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H₂O may be responsible for changing the crystallisation path.An increase in H₂O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H₂O then results in precipitation of Mt-Uv alone. The H₂O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H₂O alters the crystallisation sequence of the basaltic magmas so that at high H₂O and f（O₂） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H₂O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.     

Structure of H2O-saturated peralkaline aluminosilicate melt and coexisting aluminosilicate-saturated aqueous fluid determined in-situ to 800 °C and ∼800 MPa

The structure of H₂O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na₂O•4SiO₂-Na₂O•4(NaAl)O₂-H₂O (5 and 10 mol% Al₂O₃, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H₂O at nominal densities (from PVT properties of pure H₂O) of 0.85 g/cm³ (NA10 experiments) and 0.86 g/cm³ (NA5 experiments) with the aluminosilicate + H₂O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H₂O (H₂O°) and OH groups that form bonds with cations exist in all three phases. The OH/H₂O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H₂O, f_H2O) with (OH/H₂O°)^melt > (OH/H₂O°)^fluid at all pressures and temperatures. Structural units of Q³, Q², Q¹, and Q⁰ type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q⁰ and Q¹ increases and Q² and Q³ decrease with f_H2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of f_H2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to f_H2O.The melt structural data are used to describe relationships between activity of H₂O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qⁿ-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H₂O content.     

Crystal chemistry of selenates with mineral-like structures. VI. Hydrogen bonds in the crystal structure of [(H5O2)(H3O)(H2O)][(UO2)(SeO4)2]

The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) Å, β = 103.880(13)°, V = 1182.4(3) ų), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]^2? sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the ( $ \bar 1 The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) ?, β = 103.880(13)°, V = 1182.4(3) ?³), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]²⁻ sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (01) plane. Oxonium ions and water molecules forming [(H₃O)·(H₂O)·(H₅O₂)]²⁺ complexes are interlayer. Among minerals, the existence of (H₅O₂)⁺ has been unambiguously confirmed only in rhomboclase, (H₅O₂)⁺[Fe₂(SO₄)₂(H₂O)₂]. Original Russian Text ? S.V. Krivovichev, 2008, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2008, No. 2, pp. 123–130.     

Crystal and molecular structure and spectroscopic behavior of isotypic synthetic analogs of the oxalate minerals stepanovite and zhemchuzhnikovite

The crystal structure of synthetic stepanovite, Na[Mg(H₂O)₆][Fe(C₂O₄)₃]·3H₂O, and zhemchuzhnikovite, Na[Mg(H₂O)₆][Al_0.55Fe_0.45(C₂O₄)₃]·3H₂O, has been determined by single-crystal X-ray diffraction methods. The compounds are isotypic to each other and to the previously reported Na[Mg(H₂O)₆][M(C₂O₄)₃]·3H₂O (M: Cr, Al). They crystallize in the trigonal P3c1 space group with Z = 6 molecules per unit cell and (hexagonal axes) a = 17.0483(4), c = 12.4218(4) Å for the iron compound, and a = 16.8852(5), c = 12.5368(5) Å for the Al/Fe solid solution. Comparison of our crystallographic results with previous X-ray diffraction and chemical data of type stepanovite and zhemchuzhnikovite minerals provides compelling evidence that these natural materials possess the same crystal and molecular structure as their synthetic counterparts. It is shown that the originally reported unit cell for stepanovite represents a pronounced sub-cell and that the correct unit cell and space group are based on weak superstructure reflections. The infrared and Raman spectra of both synthetic analogs were also recorded and are briefly discussed.     

Water and magmas; a mixing model

A model for the mixing of H₂O and silicate melts has been derived from the experimentally determined effects of H₂O on the viscosity (fluidity), volumes, electrical conductivities, and especially the thermodynamic properties of hydrous aluminosilicate melts. It involves primarily the reaction of H₂O with those O^?2 ions of the melt that are shared (bridging) between adjacent (Al, Si)O₄ tetrahedra to produce OH^? ions. However, in those melts that contain trivalent ions in tetrahedral coordination, such as the Al³⁺ ion in feldspathic melts, the model further involves exchange of a proton from H₂O with a non-tetrahedrally coordinated cation that must be present to balance the net charge on the AlO₄ group. This cation exchange reaction, which goes essentially to completion, results in dissociation of the H₂O and is limited only by the availability of H₂O and the number of exchangeable cations per mole of aluminosilicate.In the system NaAlSi₃O₈-H₂O, upon which this thermodynamic model is based, there is 1 mole of exchangeable cations (Na⁺) per mole (GFW) of NaAlSi₃O₈, consequently ion exchange occurs for H₂O contents up to a 1:1 mole ratio (X^m_w = mole fraction H₂O = 0.5). For mole fractions of H₂O greater than 0.5, no further exchange can occur and the reaction with additional bridging oxygens of the melt produces 2 moles of associated OH^? ions per mole of H₂O dissolved. These reactions lead to a linear dependence of the thermodynamic activity of H₂O (a^m_w) on the square of its mole fraction (X^m_w) for values of X^m_w, up to 0.5 and an exponential dependence on X^m_w at higher H₂O contents. Thus, for values of $\text{X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{? 0.5, a}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{= k(X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{)}{}^2$, where k is a Henry's law constant for the dissociated solute.Extension of the thermodynamic model for NaAlSi₃O₈-H₂O to predict H₂O solubilities and other behavior of compositionally more complex aluminosilicate melts (magmas) requires placing these melts on an equimolal basis with NaAlSi₃O₈. This is readily accomplished using chemical analyses of quenched glasses by normalizing to the stoichiometric requirements of NaAlSi₃O₈, first in terms of equal numbers of exchangeable cations for mole fractions of H₂O up to 0.5 and secondly in terms of 8 moles of oxygen for higher H₂O contents. Chemical analyses of three igneous-rock glasses, ranging in composition from tholeiitic basalt to lithium-rich pegmatite, were thus recast and the experimental H₂O solubilities were computed on this equimolal basis. The resulting equimolal solubilities are all the same, within experimental error, as the solubility of H₂O in NaAlSi₃O₈ melt calculated from the thermodynamic relations.The equivalence of equimolal solubilities implies that the Henry's law constant (k), which is a function of temperature and pressure, is independent of aluminosilicate composition over a wide range. Moreover, as a consequence of the Gibbs-Duhem relation and the properties of exact differentials, it is clear that the silicate components of the melt, properly defined, mix ideally. Thus, a relatively simple mixing model for H₂O in silicate melts has led to a quantitative thermodynamic model for magmas that has far-reaching consequences in igneous petrogenesis.     

Water diffusion in dacitic melt

H₂O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H₂O_t). H₂O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H₂O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H₂O diffusion at high pressure is systematically slower. H₂O diffusion profiles in dacite can be modeled by assuming molecular H₂O (H₂O_m) is the diffusing species. Total H₂O diffusivity D_H2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H₂O_t can be expressed as: where D_H2Ot is in m²/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H₂O_m+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H₂O_t, and 18.015 and 33.82 g/mol correspond to the molar masses of H₂O and anhydrous dacite on a single oxygen basis. Compared to H₂O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H₂O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.     

Thermodynamic description of equilibria in mixed fluids (H2O-non-polar gas) over a wide range of temperature (25–700°C) and pressure (1–5000 bars)

A new method for computing complicated equilibria in hydrothermal mixed fluids, H₂O-non-polar gas, is proposed. The computation algorithm is based on the electrostatic approach for the interaction between aqueous species and H₂O. The approach uses the SUPCRT92 database and the HKF format and may be considered as an application of the revised HKF model for mixed H₂O-non-polar gas fluids. Thermodynamic properties of dissolved gases at high temperatures and pressures are calculated using the Redlich-Kwong approach. Dielectric permittivity of the mixed solvent is estimated by the modified Kirkwood equation.The proposed approach is validated using available experimental data on the dissociation constants of H₂O and NaCl and the solubility of both covalent and ion crystals (SiO₂, AgCl, Ag₂SO₄, Ca(OH)₂, CaCO₃) in H₂O-non-polar component (dioxane, Ar, CO₂) mixtures. Predicted and experimental data are in close agreement over a wide range of P-T-x_gas conditions (up to 500°C, 4 kbar and 0.25–0.3 mole fraction of non-polar gas). It is also shown how the computation method can be applied to estimate the Born parameters of aqueous species.The proposed approach enables not only examination of isolated reactions, but the study of equilibria of whole systems. Thus, it allows modelling of mixed natural fluids.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores. X. thermal stability and dehydration features of synthetic analogs of the cobaltomenite–ahlfeldite solid solution series

The aim of this study is the experimental investigation of the synthetic analogs of cobaltomenite, CoSeO₃ ? 2H₂O, ahlfeldite, NiSeO₃ ? 2H₂O, members of the cobaltomenite–ahlfeldite solid solution series (Ni _x Co_1–x )SeO₃ ? 2H₂O, and singularities of their dehydration and dissociation. The intermediate members of the cobaltomenite (CoSeO₃ ? 2H₂O)–ahlfeldite (NiSeO₃ ? 2H₂O) series have been synthesized and studied with a combination of X-ray diffraction, scanning electron microscopy, and the simultaneous application of thermogravimetry (TG) and differential scanning calorimetry (DSC) within the temperature range from 25 to 640°C. The complete solid solution series corresponds to the monoclinic space group P2₁/n. Unit-cell dimensions decrease in all crystallographic directions as the amount of Ni increases. The angle β increases from 98.82(1) (cobaltomenite) to 99.05(1)° (ahlfeldite). It has been established that CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O dehydrate at 120–340°C through two stages apparently corresponding, to the formation of intermediate hydrated species CoSeO₃ ? H₂O and NiSeO₃ ? 1/3H₂O. The reaction enthalpies for each dehydration stage of CoSeO₃ ? 2H₂O and NiSeO₃ ? 2H₂O have been determined. Changes of the unit-cell dimensions and dehydration temperatures are rationalized in terms of the Co and Ni site occupancy in the structure of the cobaltomenite–ahlfeldite solid-solution series members.     

Thermodynamics of ice polymorphs and ‘ice-like’ water in hydrates and hydroxides

Thermodynamic properties of water, in various families of hydroxides, oxihydroxides and hydrates (chlorides, chlorates, sulfates and sulfites …), have been calculated by using a large number of data available in the literature. A phase diagram of water has been used to find the first complete set of thermodynamic properties at 298 K, 1 bar of 8 ice polymorphs, from Ih (hexagonal ice, the common polymorph) to IX (very low temperature and high pressure polymorph). These results are used to illustrate the concept of ‘ice-like water’ available for a very large number of hydrated phases (noted X.H₂O) in which water is attached to the corresponding anhydrous substrate (noted X) within a large spectrum of different enthalpies (Δ_fH°) or Gibbs free energies (Δ_fG°), but within a relatively small range of others properties. Heat capacity (Cp°), entropy (S°), and volume (V°) of hydration water (X.H₂O−X=H₂O) appeared to be very close to those characterizing ice polymorphs such as ice II or ice VIII. This concept allows the authors to propose a classification of minerals in terms of affinity for water and to predict the relative stability of hydrated and dehydrated phases under climatic variations.     

CO2-H2O mixtures in the geological sequestration of CO2. I. Assessment and calculation of mutual solubilities from 12 to 100°C and up to 600 bar

Evaluating the feasibility of CO₂ geologic sequestration requires the use of pressure-temperature-composition (P-T-X) data for mixtures of CO₂ and H₂O at moderate pressures and temperatures (typically below 500 bar and below 100°C). For this purpose, published experimental P-T-X data in this temperature and pressure range are reviewed. These data cover the two-phase region where a CO₂-rich phase (generally gas) and an H₂O-rich liquid coexist and are reported as the mutual solubilities of H₂O and CO₂ in the two coexisting phases. For the most part, mutual solubilities reported from various sources are in good agreement. In this paper, a noniterative procedure is presented to calculate the composition of the compressed CO₂ and liquid H₂O phases at equilibrium, based on equating chemical potentials and using the Redlich-Kwong equation of state to express departure from ideal behavior. The procedure is an extension of that used by King et al. (1992), covering a broader range of temperatures and experimental data than those authors, and is readily expandable to a nonideal liquid phase. The calculation method and formulation are kept as simple as possible to avoid degrading the performance of numerical models of water-CO₂ flows for which they are intended. The method is implemented in a computer routine, and inverse modeling is used to determine, simultaneously, (1) new Redlich-Kwong parameters for the CO₂-H₂O mixture, and (2) aqueous solubility constants for gaseous and liquid CO₂ as a function of temperature. In doing so, mutual solubilities of H₂O from 15 to 100°C and CO₂ from 12 to 110°C and up to 600 bar are generally reproduced within a few percent of experimental values. Fugacity coefficients of pure CO₂ are reproduced mostly within one percent of published reference data.     

Depmeierite Na8[Al6Si6O24](PO4,CO3)1−x · 3H2O (x < 0.5): A new cancrinite-group mineral species from the Lovozero alkaline pluton of the Kola Peninsula

A new mineral depmeierite, the first cancrinite-group member with the species-forming extraframework anion PO ₄ ^3? , has been found at Mt. Karnasurt in the Lovozero alkaline pluton on the Kola Peninsula in Russia. Natrolite and depmeierite are the major components of a hydrothermal peralkaline veinlet 1.5 cm thick, which cross cuts the foyaite-urtite-lujavrite complex. The associated minerals are steenstrupine-(Ce), vuonnemite, epistolite, sodalite, aegirine, serandite, natisite, and vitusite-(Ce). Depmeierite occurs as colorless transparent isometric grains up to 1 cm in size. Its luster is vitreous. The mineral is brittle, and its cleavage (100) is perfect. Its Mohs hardness is 5, and D(meas) = 2.321(1) and D(calc) = 2.313 g/cm³. Depmeierite is optically biaxial positive, ω = 1.493(2), and ? = 1.497(2). The IR spectrum is given. The chemical composition is as follows (wt %, the average of 10 microprobe analyses with the H₂O and CO₂ determined by selective sorption): 23.04 Na₂O, 0.54 K₂O, 0.03 Fe₂O₃, 29.07 Al₂O₃, 36.48 SiO₂, 3.30 P₂O₅, 0.08 SO₃, 0.97 CO₂, and 5.93 H₂O; the total is 99.44. The empirical formula based on (Si,Al)₁₂O₂₄ is (Na₇₅₈K_0.12)_Σ7.70(Si_6.19Al_5.81O₂₄)[(PO₄)_0.47(CO₃)_0.22(OH)_0.02(SO₄)_0.01]_Σ0.72 · 3.345H₂O. The simplified formula is Na₈[Al₆Si₆O₂₄](CO₃)_{1 ? x} · 3H₂O (x < 0.05). Depmeierite is hexagonal with space group P6₃, and the unit-cell dimensions are a = 12.7345(2), c = 5.1798(1), V = 727.46(2) ų, and Z = 1. The strongest reflections of the X-ray powder pattern (d, Å (I, %) [hkl]) are as follows: 6.380(30) [110], 4.695(91) [101], 3.681(37) [300], 3.250(100) [211], 2.758 (33) [400], 2.596(31) [002], and 2.121(24) [330, 302]. The crystal structure was studied using a single crystal, and R _hkl = 0.0362. Depmeierite differs from cancrinite in the development of wide channels containing Na cations, H₂O molecules, prevailing PO ₄ ^3? -anionic groups, and CO ₃ ^2? . The mineral is named in honor of the German crystallographer Wulf Depmeier (born in 1944). The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences in Moscow. The cancrinite sensu stricto subgroup separated within the cancrinite group comprises six minerals with AB frameworks, the smallest unit cell is (a ≈ 12.55–12.75, c ≈ 5.1–5.4 Å), and the chain […Na…H₂O…]^∞ exists in narrow channels: cancrinite, vishnevite, cancrisilite, hydroxycancrinite, kyanoxalite, and depmeierite. The P-bearing varieties of the cancrinite-group minerals are discussed, as well as the formation conditions of the noncarbonate members of the group related to intrusive alkaline complexes.     

Solubilities of corundum, wollastonite and quartz in H2O-NaCl solutions at 800 °C and 10 kbar: Interaction of simple minerals with brines at high pressure and temperature

Solubilities of corundum (Al₂O₃) and wollastonite (CaSiO₃) were measured in H₂O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H₂O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al₂O₃ molality (m_Al2O3) of 0.0013(1) (1σ error) in pure H₂O and then leveling off to a maximum of ∼0.015 at halite saturation (X_NaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H₂O, , passes through a maximum at X_NaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H₂O at this P and T(m_CaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H₂O at X_NaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H₂O-NaCl-SiO₂, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from m_SiO2=1.248 in pure H₂O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H₂O reproduces the data and indicates that hydrogen bonding of molecular H₂O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na⁺ and/or Cl⁻ species produced by molar ratios of reactant H₂O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.     

Crystal chemistry of selenates with mineral-like structures. III. Heteropolyhedral chains in the crystal structure of [Mg(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(SeO<Subscript>4</Subscript>)]<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)

The crystal structure of a new compound [Mg(H₂O)₄(SeO₄)]₂(H₂O) (monoclinic, P2 ₁/a, a = 7.2549(12), b = 20.059(5), c = 10.3934(17) Å, β = 101.989(13), V = 1479.5(5) ų) has been solved by direct methods and refined to R ₁ = 0.059 for 2577 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure consists of [Mg(H₂O)₄(SeO₄)]⁰ chains formed by alternating corner-sharing Mg octahedrons and (SeO₄)^2? tetrahedrons. O atoms of Mg octahedrons that are shared with selenate tetrahedrons are in a trans orientation. The heteropoly-hedral octahedral-tetrahedral chains are parallel to the c axis and undulate within the (010) plane. The adjacent chains are linked by hydrogen bonds involving H₂O molecules not bound with M²⁺ cations.     

Hydrogen bonding in coquimbite, nominally Fe2(SO4)3·9H2O, and the relationship between coquimbite and paracoquimbite

Using single-crystal X-ray diffraction at 293, 200 and 100 K, and neutron diffraction at 50 K, we have refined the positions of all atoms, including hydrogen atoms (previously undetermined), in the structure of coquimbite ( $ P {\bar 3}1c $ , a?=?10.924(2)/10.882(2) Å, c?=?17.086(3) / 17.154(3) Å, V?=?1765.8(3)/1759.2(5) ų, at 293 / 50 K, respectively). The use of neutron diffraction allowed us to determine precise and accurate hydrogen positions. The O–H distances in coquimbite at 50 K vary between 0.98 and 1.01 Å. In addition to H₂O molecules coordinated to the Al³⁺ and Fe³⁺ ions, there are rings of six “free” H₂O molecules in the coquimbite structure. These rings can be visualized as flattened octahedra with the distance between oxygen and the geometric center of the polyhedron of 2.46 Å. The hydrogen-bonding scheme undergoes no changes with decreasing temperature and the unit cell shrinks linearly from 293 to 100 K. A review of the available data on coquimbite and its “dimorph” paracoquimbite indicates that paracoquimbite may form in phases closer to the nominal composition of Fe₂(SO₄)₃·9H₂O. Coquimbite, on the other hand, has a composition approximating Fe_1.5Al_0.5(SO₄)₃·9H₂O. Hence, even a “simple” sulfate Fe_2-x Al _x (SO₄)₃·9H₂O may be structurally rather complex.     

Spectroscopic analysis (FTIR, Raman) of water in mafic and intermediate glasses and glass inclusions

Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H₂O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH⁻ and molecular H₂O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H₂O content (H₂O_T = OH⁻ + H₂O_m) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm⁻¹ band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H₂O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H₂O_T band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H₂O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H₂O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm⁻¹. We provide new FTIR absorptivity coefficients (ε₃₅₅₀) for basalt (62.80 ± 0.8 L mol⁻¹ cm⁻¹) and basanite (43.96 ± 0.6 L mol⁻¹ cm⁻¹). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε₃₅₅₀) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H₂O in silicate glasses when the matrix effects are properly considered.     

Miscibility in the CaSO4·2H2O–CaSeO4·2H2O system: Implications for the crystallisation and dehydration behaviour

SeO₄²⁻ ions can substitute for sulphate in the gypsum structure. In this work crystals of different Ca(SO₄,SeO₄)·2H₂O solid solutions were precipitated by mixing a CaCl₂ solution with solutions containing different ratios of Na₂SO₄ and Na₂SeO₄. The compositions of the precipitates were analysed by EDS and the cell parameters were determined by X-ray powder diffraction. Moreover, a comparative study on dehydration behaviour of selenate rich and sulfate rich Ca(SO₄,SeO₄)·2H₂O solid solutions was carried out by thermogravimetry.The experimental results show that the Ca(SO₄,SeO₄)·2H₂O solid solution presents a symmetric miscibility gap for compositions ranging from X_CaSO4·2H2O = 0.23 to X_CaSO4·2H2O = 0.77. By considering a regular solution model a Guggenheim parameter a₀ = 2.238 was calculated. The solid phase activity coefficients obtained with this parameter were used to calculate a Lippmann diagram for the system Ca(SO₄,SeO₄)·2H₂O–H₂O.