Atomistic model of diopside-K-jadeite (CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>-KAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>) solid solution

Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi₂O6-KAlSi₂O₆). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi₂O₆ and KAlSi₂O₆ and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023 K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi₂O₆-KAlSi₂O₆ at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties of K-jadeite (KAlSi₂O₆) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi₂O₆ in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively high standard enthalpy of this end member.     

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).     

Vibrational states of H<Subscript>2</Subscript>O in beryl: physical aspects

Single-crystal polarized Raman spectra (3,000–4,000 cm⁻¹ at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be₂Al₃Si₆O₁₈·xH₂O, to determine the behavior of H₂O molecules of both Type I and Type II in the cavities. At low temperature, the H₂O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H₂O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm⁻¹. Water Type II is characterized by a free rotation with respect to the C ₂ molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.

First-principles-based calculations of the CaCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> and CdCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> subsolidus phase diagrams

 Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of the CaCO₃–MgCO₃ and CdCO₃–MgCO₃ phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved phases, Cd₃Mg (CO₃)₄ and CdMg₃(CO₃)₄, are predicted. No new phases are predicted in the CaCO₃–MgCO₃ system, but a low-lying metastable Ca₃Mg(CO₃)₄ state, analogous to the Cd₃Mg(CO₃)₄ phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg₃(CO₃)₄, have dolomite-related structures, i.e. they are layer structures in which A _m B _n cation layers lie perpendicular to the rhombohedral [111] vector. Received: 6 May 2002 / Accepted: 23 October 2002 Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST.     

Thermodynamics of mixing in diopside–jadeite,CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>, solid solution from static lattice energy calculations

Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800 different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440, 1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral 83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C.     

The H<Subscript>2</Subscript>O solubility of alkali basaltic melts: an experimental study

Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes, Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model for the water solubility of basalts of varying alkalinity and fO₂ to be derived: \textH ₂ \textO( \textwt% ) = \text H ₂ \textO_\textMORB ( \textwt% ) + ( 5.84 ×10 ^{- 5} *\textP - 2.29 ×10 ^{- 2} ) ×( \textNa₂ \textO + \textK₂ \textO )( \textwt% ) + 4.67 ×10 ^{- 2} ×\Updelta \textNNO - 2.29 ×10 ^{- 1} {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H₂O_MORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents, whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using standard thermodynamic considerations yields values close to previous findings if room temperature water species are used. When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation of the partial molar volume of total water using H₂O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm³/mol in reasonable agreement with estimates obtained from density measurements.     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

Theoretical studies of cation adsorption on hydroxylated α-A1<Subscript>2</Subscript>O<Subscript>3</Subscript> (corundum): electronic structure calculations

 The adsorption of alkali metal cations on a hydroxylated corundum surface was investigated using high-level electronic structure calculations, with both cluster Hartree–Fock and periodic density-functional theory approaches. The work concentrates on the structural aspects of binding sites with threefold oxygen coordination at the basal (0001) surface. It was found that adsorption at different sites can give rise to a wide range of adsorption energies, which strongly depends on the freedom of surface hydrogen atoms to adjust their positions. Alkali metal adions from Li⁺ to Cs⁺ were studied with the cluster method, periodic plane-wave pseudopotential calculations being carried out for K⁺ adsorption to validate the cluster results. A site above an octahedral interstice was found to be the least preferred for cation adsorption, despite having the lowest repulsion from surface aluminium atoms. The strongest adsorption was found over an aluminium atom in the second layer, because the hydroxyl groups could reorient towards the neighbouring octahedral interstices, and hence significantly decrease repulsion with the cation. The adsorption energy and the first three interlayer spacings parallel to the basal surface change systematically with ionic size for each adsorption site. Many of these trends extend to adsorption of Ca²⁺, Co²⁺ and Pb²⁺, which were also investigated, although a redistribution of 3d electrons in Co²⁺ results in strong adsorption even at an unfavourable site. The results suggest that it may be possible not only to predict adsorption behaviour for a wide range of elements, but also to use experimental measurements of interplanar separations to gain information about contaminated surfaces. Received: 29 April 2002 / Accepted: 23 October 2002 Acknowledgements The authors thank the Natural Environment Research Council for support in carrying out this work.     

Single-crystal Raman spectra of YAlO<Subscript>3</Subscript> and GdAlO<Subscript>3</Subscript>: comparison to several orthorhombic ABO<Subscript>3</Subscript> perovskites

Room-temperature-polarized single-crystal Raman spectra have been measured for both GdAlO₃ and YAlO₃. Both aluminates crystallize in the orthorhombic (Pbnm) perovskite structure. Of the 24 possible Raman modes in 4 symmetries, 20 and 17 modes were observed for gadolinium and yttrium aluminates, respectively. Comparisons of the Raman spectra of these two aluminates to those of 28 other orthorhombic ABO₃ perovskites revealed remarkably similar spectral patterns, regardless of chemistry or valency of the cations. Closer examination of the effect of mass, valencies, and size of the cations on the Raman spectra versus composition revealed that for the observed modes, the A cation plays the dominant role in determining the Raman shift. In particular, the one to two lowest energy modes in each symmetry are determined by cation mass and valency no matter what the chemistry. For some perovskites with common A cations, higher energy modes were also strikingly similar. In particular, the calcium perovskites had almost all A_g modes at the same energies despite the greatly varying B cations. The second to the lowest mode in A_g and B_1g depended only on A cation mass for all perovskites. The volume plays a minor role throughout but is hard to separate from mass effects because the most massive cations are also the largest. However, if the B-cation is common, for example, aluminates or ferrites, the volume has a minor effect on the higher energy modes. These trends were not observed for all perovskites. Notable exceptions were found if a perovskite is near a phase transition or metastable, as found for three manganites. The effect of increased valency of the A cation from 2–4 to 3–3 perovskites expresses itself as relatively larger Raman shifts for the lowest energy modes. Analog studies of MgSiO₃ perovskites should be undertaken with only 2–4 perovskites. The increased understanding for the mode distributions of perovskites allows for better estimates of their thermodynamic properties through vibrational modeling.     

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.     

Experimental multipole-refined and theoretical charge density study of LiGaSi<Subscript>2</Subscript>O<Subscript>6</Subscript> clinopyroxene at ambient conditions

The synthetic LiGaSi₂O₆ clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi₂O₆), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si₂O₆ group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Pressure and temperature dependence of the viscosity of a NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript> melt

The viscosity of a silicate melt of composition NaAlSi₂O₆ was measured at pressures from 1.6 to 5.5 GPa and at temperatures from 1,350 to 1,880°C. We employed in situ falling sphere viscometry using X-ray radiography. We found that the viscosity of the NaAlSi₂O₆ melt decreased with increasing pressure up to 2 GPa. The pressure dependence of viscosity is diminished above 2 GPa. By using the relationship between the logarithm of viscosity and the reciprocal temperature, the activation energies for viscous flow were calculated to be 3.7 ± 0.4 × 10² and 3.7 ± 0.5 × 10² kJ/mol at 2.2 and 2.9 GPa, respectively.     

H<Subscript>2</Subscript>O storage capacity of olivine and low-Ca pyroxene from 10 to 13 GPa: consequences for dehydration melting above the transition zone

The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H₂O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H₂O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H₂O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H₂O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation C_{\textH2 \textO}^\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of D_{\textH2 \textO}^{\textpyx/olivine} D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of D_{\textH2 \textO}^{\textgt/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H₂O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H₂O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H₂O, can exceed the peridotite H₂O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of D_{\textH2 \textO}^{\textpyx/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H₂O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.     

Equation of state and crystal structure of Sb<Subscript>2</Subscript>S<Subscript>3</Subscript> between 0 and 10 GPa

High-precision unit-cell volume data of stibnite, collected in the pressure range of 0–10 GPa, was used for fitting a third-order Birch–Murnaghan equation of state. The zero-pressure volume, bulk modulus and its pressure derivative were found to be 487.73(6) ų, 26.91(14) GPa and 7.9(1), respectively. A series of X-ray intensity data was collected in the same pressure range using a CCD-equipped Bruker diffractometer. The high-pressure structures were all refined to R1(|F₀|>4) values of approximately 0.03. Crystal-chemical parameters as polyhedron volume, centroid and eccentricity were calculated for the seven coordinated cation positions using the software IVTON. The cation eccentricity appears to be a very useful tool for quantification of the lone electron pair activity. U₂S₃, Dy₂S₃ and Nd₂Te₃ are all isostructural with stibnite, but the cations in these materials have no lone electron pair. Their eccentricity is much smaller than that of Sb, and close to zero. This confirms that the stibnite structure type alone does not force eccentricity upon the cations involved and it is the lone electron pairs of Sb that generate the eccentricity of cation positions in the structures of stibnite. At increasing pressure the eccentricity of Sb is decreasing. It is therefore reasonable to conclude that the lone electron pair activity is decreasing with increasing pressure.     

Temperature-jump induced cation exchange kinetics in (Co<Subscript>0.1</Subscript>Mg<Subscript>0.9</Subscript>)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine: an in situ optical spectroscopic study

In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation exchange between the two octahedral sites in (Co_0.1Mg_0.9)₂SiO₄ single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance of Co²⁺ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump induced relaxation experiments that with increasing temperature the absorbance of Co²⁺ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co²⁺ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co_0.1Mg_0.9)₂SiO₄ olivine. Implications for cation diffusion at low temperatures are discussed.     

Single-crystal EPR and DFT studies of a [BO<Subscript>4</Subscript>]<Superscript>0</Superscript> center in datolite: electronic structure,formation mechanism and implications

A natural datolite CaBSiO₄(OH) (Bergen Hill, NJ, USA), before and after gamma-ray irradiation (up to ~70 kGy), has been investigated by single-crystal and powder electron paramagnetic resonance (EPR) spectroscopy from 10 to 295 K. EPR spectra of gamma-ray-irradiated datolite show the presence of a boron-associated oxygen hole center (BOHC) and an atomic hydrogen center (H⁰), both of which grow with increasing radiation dose. The principal g and A(¹¹B) values of the BOHC at 10 K are: g ₁ = 2.04817(3), g ₂ = 2.01179(2), g ₃ = 2.00310(2), A ₁ = −0.401(7) mT, A ₂ = −0.906(2) mT, A ₃ = −0.985(2) mT, with the orientations of the g ₁ and A ₁ axes approximately along the B–OH bond direction. These experimental results suggest that the BOHC represents hole trapping on the hydroxyl oxygen atom after the removal of the proton (i.e. a [BO₄]⁰ center): via a reaction O₃BOH → O₃BO^· + H⁰, where · denotes the unpaired electron. Density functional theory (DFT) calculations (CRYSTAL06, B3PW, all-electron basis sets, and 1 × 2 × 2 supercell) support the proposed structural model and yield the following ¹¹B hyperfine coupling constants: A ₁ = −0.429 mT, A ₂ = −0.901 mT, A ₃ = −0.954 mT, in excellent agreement with the experimental results. The [BO₄]⁰ center undergoes the onset of thermal decay at ~200°C and is completely annealed out at 375°C but can be restored readily by gamma-ray irradiation. Isothermal annealing experiments show that the [BO₄]⁰ center exhibits a second-order thermal decay with an activation energy of 0.96 eV. The confirmation of the [BO₄]⁰ center (and its formation from the O₃BOH precursor) in datolite has implications for not only understanding of BOHCs in alkali borosilicate glasses but also their applications to nuclear waste disposal.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

Structure and phase transition of CaGe<Subscript>2</Subscript>O<Subscript>5</Subscript> revisited

The structure of CaGe₂O₅ between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at T_c=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e₂₃, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe₂O₅.     

Elasticity and equation of state of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

A single crystal X-ray diffraction study on lithium tetraborate Li₂B₄O₇ (diomignite, space group I4₁ cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and hence the pressure evolution of the unit-cell volume of the I4₁ cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters: V ₀  = 923.21(6) ų, K ₀  = 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a ₀  = 9.4747(3) Å, K _0a  = 73.3(9) GPa, K′ _a  = 5.1(3) and c ₀  = 10.2838(4) Å, K _0c  = 24.6(3) GPa, K′ _c  = 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li₂B₄O₇ is very large with the zero-pressure compressibility ratio β _0c /β _0a  = 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively rigid tetraborate groups [B₄O₇]²⁻ forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B₄O₇]²⁻ units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic (Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992).     

Electrical conductivity of dry and hydrous NaAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glasses and liquids at high pressures

We report the first study of electrical conductivities of silicate melts at very high pressures (up to 10 GPa) and temperatures (up to 2,173 K). Impedance spectroscopy was applied to dry and hydrous albite (NaAlSi₃O₈) glasses and liquids (with 0.02–5.7 wt% H₂O) at 473–1,773 K and 0.9–1.8 GPa in a piston-cylinder apparatus, using a coaxial cylindrical setup. Measurements were also taken at 473–2,173 K and 6–10 GPa in two multianvil presses, using simple plate geometry. The electrical conductivity of albite melts is found to increase with temperature and water content but to decrease with pressure. However, at 6 GPa, conductivity increases rapidly with temperature above 1,773 K, so that at temperatures beyond 2,200 K, conductivity may actually increase with pressure. Moreover, the effect of water in enhancing conductivity appears to be more pronounced at 6 GPa than at 1.8 GPa. These observations suggest that smaller fractions of partial melt than previously assumed may be sufficient to explain anomalously high conductivities, such as in the asthenosphere. For dry melt at 1.8 GPa, the activation energy at T > 1,073 K is higher than that at T < 1,073 K, and the inflection point coincides with the rheological glass transition. Upon heating at 6–10 GPa, dry albite glass often shows a conductivity depression starting from ~1,173 K (due to crystallization), followed by rapid conductivity enhancement when temperature approaches the albite liquidus. For hydrous melts at 0.9–1.8 GPa, the activation energies for conductivity at ≥1,373 K are lower than those at <973 K, with a complex transition pattern in between. Electrical conductivity and previously reported Na diffusivity in albite melt are consistent with the Nernst–Einstein relation, suggesting the dominance of Na transport for electrical conduction in albite melts.