Aluminum speciation, vibrational entropy and short-range order in calcium aluminosilicate glasses

The heat capacity and vibrational entropy of a calcium aluminate and three peraluminous calcium aluminosilicate glasses have been determined from 2 to 300 K by heat-pulse relaxation calorimetry. Together with previous adiabatic data for six other glasses in the system CaO-Al₂O₃-SiO₂, these results have been used to determine partial molar heat capacities and entropies for five species namely, SiO₂, CaO and three different sorts of Al₂O₃ in which Al is 4-, 5- and 6-fold coordinated by oxygen. Given the determining role of oxygen coordination on low-temperature heat capacity, the composition independent entropies found for SiO₂ and CaO indicate that short-range order around Si and Ca is not sensitive to aluminum speciation up to the highest fraction of 25% observed for ^VAl by NMR spectroscopy. Because of the higher room-temperature vibrational entropy of ^IVAl₂O₃ (72.8 J/mol K) compared to ^VAl₂O₃ (48.5 J/mol K), temperature-induced changes from ^IVAl to ^VAl give rise to a small negative contribution of the order of 1 J/mol K to the partial molar configurational heat capacity of Al₂O₃ in melts. Near 0 K, pure SiO₂ glass distinguishes itself by the importance of the calorimetric boson peak. On a g atom basis, the maximum of this peak varies with the composition of calcium aluminosilicate glasses by a factor of about 2. It does not show smooth variations, however, either as a function of SiO₂ content, at constant CaO/Al₂O₃ ratio, or as a function of Al₂O₃ content, at constant SiO₂ content.     

A calorimetric investigation of spessartine: Vibrational and magnetic heat capacity

The heat capacity (C_p) of two synthetic spessartine samples (Sps) was measured on 20-30 mg-size samples in the temperature range 2-864 K by relaxation calorimetry (RC) and differential scanning calorimetry (DSC). The polycrystalline spessartine samples were synthesized in two different laboratories at high pressures and temperatures from glass and oxide-mixture starting materials and characterized by X-ray powder diffraction and electron-microprobe analysis. The low-temperature heat capacity data show a prominent lambda transition with a peak at 6.2 K, which is interpreted to be the result of a paramagnetic-antiferromagnetic phase transition. The DSC data around ambient T agree excellently with the RC data and can be represented by the C_p polynomial for T > 250 K:

     

Molecular H2O in armenite, BaCa2Al6Si9O30·2H2O, and epididymite, Na2Be2Si6O15·H2O: Heat capacity, entropy and local-bonding behavior of confined H2O in microporous silicates

Armenite, ideal formula BaCa₂Al₆Si₉O₃₀·2H₂O, and its dehydrated analog BaCa₂Al₆Si₉O₃₀ and epididymite, ideal formula Na₂Be₂Si₆O₁₅·H₂O, and its dehydrated analog Na₂Be₂Si₆O₁₅ were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C_p, behavior of their confined H₂O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H₂O molecule.The determined structural formula for armenite is Ba_0.88(0.01)Ca_1.99(0.02)Na_0.04(0.01)Al_5.89(0.03)Si_9.12(0.02)O₃₀·2H₂O and for epididymite Na_1.88(0.03)K_0.05(0.004)Na_0.01(0.004)Be_2.02(0.008)Si_6.00(0.01)O₁₅·H₂O. The infrared (IR) spectra give information on the nature of the H₂O molecules in the natural phases via their H₂O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H₂O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔS^rxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔS^rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H₂O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H₂O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H₂O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H₂O phases ice, liquid water and steam, the C_p behavior of confined H₂O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C_p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H₂O at 298 K is analyzed for various microporous silicates.The entropy of confined H₂O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H₂O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H₂O. This results in increased amplitudes of external H₂O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H₂O at T < 298 K.     

Heat capacities of aqueous sodium hydroxide/aluminate mixtures and prediction of the solubility constant of boehmite up to 300 °C

A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg⁻¹, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, C_p?, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young’s rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, C_p? (‘NaAl(OH)₄’(aq)). Slopes of the Young’s rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of C_p? (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C.     

Temperature independent thermal expansivities of calcium aluminosilicate melts between 1150 and 1973 K in the system anorthite-wollastonite-gehlenite (An-Wo-Geh): A density model

The thermal expansivities of 10 compositions from within the anorthite-wollastonite-gehlenite (An-Wo-Geh) compatibility triangle have been investigated using a combination of calorimetry and dilatometry on the glassy and liquid samples. The volumes at room temperature were derived from densities measured using the Archimedean buoyancy method. For each sample, density was measured at 298 K using glass that had a cooling-heating history of 10-10 K min⁻¹. The thermal expansion coefficient of the glass from 298 K to the glass transition interval was measured by a dilatometer and the heat capacity was measured using a differential scanning calorimeter from 298 to 1135 K. The thermal expansion coefficient and the heat flow were determined at a heating rate of 10 K min⁻¹ on glasses which were previously cooled at 10 K min⁻¹. Supercooled liquid density, molar volume and molar thermal expansivities were indirectly determined by combining differential scanning calorimetric and dilatometric measurements assuming that the kinetics of enthalpy and shear relaxation are equivalent. The data obtained on supercooled liquids were compared to high-temperature predictions from the models of (Lange, R.A., Carmichael, I.S.E., 1987. Densities of Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ liquids: New measurements and derived partial molar properties. Geochim. Cosmochim. Acta51, 2931-2946; Courtial, P., Dingwell, D.B., 1995. Nonlinear composition dependence of molar volume of melts in the CaO-Al₂O₃-SiO₂ system. Geochim. Cosmochim. Acta59 (18), 3685-3695; Lange, R.A., 1997. A revised model for the density and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids from 700 to 1900 K: extension to crustal magmatic temperatures. Contrib. Mineral. Petrol.130, 1-11). The best linear fit combines the supercooled liquid data presented in this study and the high temperature data calculated using the Courtial and Dingwell (1995) model. This dilatometric/calorimetric method of determining supercooled liquid molar thermal expansivity greatly increases the temperature range accessible for thermal expansion. It represents a substantial increase in precision and understanding of the thermodynamics of calcium aluminosilicate melts. This enhanced precision demonstrates clearly the temperature independence of the melt expansions in the An-Wo-Geh system. This contrasts strongly with observations for neighboring system such as anorthite-diopside and raises the question of the compositional/structural origins of temperature dependence of thermal expansivity in multicomponent silicate melts.     

Influence of glass polymerisation and oxidation on micro-Raman water analysis in alumino-silicate glasses

The development of an accurate analytical procedure for determination of dissolved water in complex alumino-silicate glasses via micro-Raman analysis requires the assessment of the spectra topology dependence on glass composition. We report here a detailed study of the respective influence of bulk composition, iron oxidation state and total water content on the absolute and relative intensities of the main Raman bands related to glass network vibrations (LF: ∼490 cm⁻¹; HF: ∼960 cm⁻¹) and total water stretching (H₂O_T: ∼3550 cm⁻¹) in natural glasses. The evolution of spectra topology was examined in (i) 33 anhydrous glasses produced by the re-melting of natural rock samples, which span a very large range of polymerisation degree (NBO/T from 0.00 to 1.16), (ii) 2 sets of synthetic anhydrous basaltic glasses with variable iron oxidation state (Fe³⁺/Fe_T from 0.05 to 0.87), and (iii) 6 sets of natural hydrous glasses (C_H2OT from 0.4 to 7.0 wt%) with NBO/T varying from 0.01 to 0.76.In the explored domain of water concentration, external calibration procedure based on the H₂O_T band height is matrix-independent but its accuracy relies on precise control of the focusing depth and beam energy on the sample. Matrix-dependence strongly affects the internal calibrations based on H₂O_T height scaled to that of LF or HF bands but its effect decreases from acid (low NBO/T, SM) to basic (high NBO/T, SM) glasses. Structural parameters such as NBO/T (non-bridging oxygen per tetrahedron) and SM (sum of structural modifiers) describe the matrix-dependence better than simple compositional parameters (e.g. SiO₂, Na₂O + K₂O). Iron oxidation state has only a minor influence on band topology in basalts and is thus not expected to significantly affect the Raman determinations of water in mafic (e.g. low SiO₂, iron-rich) glasses. Modelling the evolution of the relative band height with polymerisation degree allows us to propose a general equation to predict the dissolved water content in natural glasses:

     

Thermodynamic properties of chlorite CCa-2. Heat capacities, heat contents and entropies

The heat capacities of the international reference clay mineral chlorite CCa-2 from Flagstaff Hill, California, were measured by low temperature adiabatic calorimetry and differential scanning calorimetry, from 5 to 520 K (at 1 bar). The studied chlorite is a Fe-bearing trioctahedral chlorite with an intermediary composition between ideal clinochlore (Si₃Al)(Mg₅Al)O₁₀(OH)₈ and chamosite (Si₃Al)(Fe₅Al)O₁₀(OH)₈. Only few TiO₂ impurities were detected in the natural chlorite sample CCa-2. Its structural formula, obtained after subtracting the remaining TiO₂ impurities, is (Si_2.633Al_1.367)(Al_1.116Mg_2.952Mn_0.012Ca_0.011)O₁₀(OH)₈. From the heat capacity results, the entropy, standard entropy of formation and heat content of the chlorite were deduced. At 298.15 K, the heat capacity of the chlorite is 547.02 (±0.27) J mol⁻¹ K⁻¹ and the molar entropy is 469.4 (±2.9) J mol⁻¹ K⁻¹. The standard molar entropy of formation of the clay mineral from the elements is −2169.4 (±4.0) J mol⁻¹ K⁻¹.     

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.     

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

     

An experimental investigation on diffusion of water in haplogranitic melts

  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz₂₈Ab₃₈Or₃₄ (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D _water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D _water with pressure indicates an average activation volume of about 9 cm³/mole. The diffusivity (in cm²/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by

Determination of hydrogen content in geological samples using elastic recoil detection analysis (ERDA)

The present study illustrates the interest of using the elastic recoil detection analysis (ERDA) method to characterize any geological sample matrix with respect to hydrogen. ERDA is combined with Rutherford back scattering (RBS) and particle induced X-ray emission (PIXE), allowing the simultaneous characterization of the matrix with respect to major and trace elements (Z > 15). Analyses are performed by mapping of a 4 × 16 μm² incident beam of ⁴He⁺ on large areas (50 × 200 μm²). The method is almost not destructive and requires no calibration with respect to well known hydrous samples. Hydrous and nominally anhydrous phases in contact with each other in the same sample may both be characterized. The depth of the analyses is limited to several μm beneath the surface, allowing tiny samples to be investigated, provided their sizes are larger than the incident beam. Our setup has been improved in order to allow H determination on a micrometric scale with a 5-15% relative uncertainty and a detection limit of 94 wt ppm H₂O. We present multi-elemental mappings on a large panel of samples: (1) natural and analogue synthetic glasses from Stromboli volcano (0.44-4.59 wt% H₂O), natural rhyolitic glasses (1466-1616 wt ppm H₂O); (2) magmatic rhyolitic melt inclusions from Guadeloupe Island (4.37-5.47 wt% H₂O) and their quartz host crystal (2020 ± 230 wt ppm H₂O); (3) nominally anhydrous natural (82-260 wt ppm H₂O) and experimentally hydrated (240-790 wt ppm H₂O) olivines; natural clinopyroxenes (159-716 wt ppm H₂O); natural orthopyroxenes (201-452 wt ppm H₂O); a natural garnet (90 wt ppm H₂O). Results show that ERDA is a strong and accurate reference method that can be used to characterize geological sample from various matrix compositions from high to low water contents. It can be used to calibrate other methods of microanalysis such as Fourier Transform Infrared Spectroscopy (FTIR) or secondary ion mass spectrometry (SIMS).     

Acoustic velocity measurements on Na2O-TiO2-SiO2 liquids: Evidence for a highly compressible TiO2 component related to five-coordinated Ti

Longitudinal acoustic velocities were measured at 1 bar in 10 Na₂O-TiO₂-SiO₂ (NTS) liquids for which previous density and thermal expansion data are reported in the literature. Data were collected with a frequency-sweep acoustic interferometer at centered frequencies of 4.5, 5, and 6 MHz between 1233 and 1896 K; in all cases, the sound speeds decrease with increasing temperature. Six of the liquids have a similar TiO₂ concentration (∼25 mol %), so that the effect of varying Na/Si ratio on the partial molar compressibility of the TiO₂ component can be evaluated. Theoretically based models for β_T and (∂V/∂P)_T as a function of composition and temperature are presented. As found previously for the partial molar volume of TiO₂ in sodium silicate melts, values of (13.7-18.8 × 10⁻²/GPa) vary systematically with the Na/Si and Na/(Si + Ti) ratio in the liquid. In contrast values of for the SiO₂ and Na₂O components (6.6 and 8.0 × 10⁻²/GPa, respectively, at 1573 K) are independent of composition. Na₂O is the only component that contributes to the temperature dependence of the compressibility of NTS liquids (1.13 ± 0.04 × 10⁻⁴/GPa K). The results further indicate that the TiO₂ component is twice as compressible as the Na₂O and SiO₂ components. The enhanced compressibility of TiO₂ appears to be related to the abundance of five-coordinated Ti (^[5]Ti) in these liquids, but not with a change in Ti coordination. Instead, it is proposed that the asymmetric geometry of ^[5]Ti in a square pyramidal site promotes different topological rearrangements in alkali titanosilicate liquids, which lead to the enhanced compressibility of TiO₂.     

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.     

The effect of Al3+, Fe3+, and Ti4+ on the configurational heat capacities of sodium silicate liquids

The heat capacities of 29 glasses and supercooled liquids in the Na₂O-SiO₂, Na₂O-Al₂O₃-SiO₂, Na₂O-(FeO)-Fe₂O₃-SiO₂, and Na₂O-TiO₂-SiO₂ systems were measured in air from 328 to 998 K with a differential scanning calorimeter. The reproducibility of the data determined from multiple heat capacity runs on a single crystal MgO standard is within ± 1% of the accepted values at temperatures ≤ 800 K and within ± 1.5% between 800 and 1000 K. Within the resolution of the data, the heat capacities of sodium silicate and sodium aluminosilicate liquids are temperature independent. Heat capacity data in the supercooled liquid region for the sodium silicates and sodium aluminosilicates were combined and modelled assuming a linear compositional dependence. The derived values for the partial molar heat capacities of Na₂O, Al₂O₃, and SiO₂ are 112.35 ± 0.42, 153.16 ± 0.82, and 76.38 ± 0.20 J/gfw · K respectively. The partial molar heat capacities of Fe₂O₃ and TiO₂ could not be determined in the same manner because the heat capacities of the Fe₂O₃- and TiO₂-bearing sodium silicate melts showed varying degrees of negative temperature dependence. The negative temperature dependence to the configurational C _P may be related to the occurrence of sub-microscopic domains (relatively polymerized and depolymerized) that break down to a more homogeneous melt structure with increasing temperature. Such an interpretation is consistent with data from in situ Raman, Mössbauer, and X-ray absorption fine structure (XAFS) spectroscopic studies on similar melts.     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.     

Entropy and structure of oxidized and reduced iron-bearing silicate glasses

The influence of ferrous and ferric iron on the low-temperature heat capacity and vibrational entropy of silicate glasses has been determined by adiabatic calorimetry. Two pairs of samples based on sodium disilicate and calcium Tschermak molecule compositions have been studied. Along with previous data for another Fe-bearing glass, these results have been used to complement the available set of composition independent partial molar relative entropies of oxides in silicate glasses with S₂₉₈ − S₀ values of 56.7 and 116 J/mol for FeO and Fe₂O₃, respectively. The calorimetric data indicate that the fraction of fivefold coordinated Al is significant in the CaO-“FeO”-Al₂O₃-SiO₂ system and that association of Ca²⁺ and Na⁺ with Fe³⁺ in tetrahedral coordination for charge compensation does not entail significant changes in coordination for these two cations. At very low temperatures, however, the heat capacity is no longer an additive function of composition because of unexpectedly high positive deviations from Debye laws. These anomalies are stronger for the reduced than the oxidized glasses and considerably larger than for iron-free glasses, but their origin cannot be established from the present measurements.     

Quantification of water content and speciation in natural silicic glasses (phonolite, dacite, rhyolite) by confocal microRaman spectrometry

The determination of total water content (H₂O_T: 0.1-10 wt%) and water speciation (H₂O_molecular/OH) in volcanic products by confocal microRaman spectrometry are discussed for alkaline (phonolite) and calcalkaline (dacite and rhyolite) silicic glasses. Shape and spectral distribution of the total water band (H₂O_T) at ∼3550 cm⁻¹ show systematic evolution with glass H₂O_T, water speciation and NBO/T. In the studied set of silicic samples, calibrations based on internal normalization of the H₂O_T band to a band related to vibration of aluminosilicate network (TOT) at ∼490 cm⁻¹ vary with glass peraluminosity. An external calibration procedure using well-characterized glass standards is less composition-dependent and provides excellent linear correlation between total dissolved water content and height or area of the H₂O_T Raman band. Accuracy of deconvolution procedure of the H₂O_T band to quantify water speciation in water-rich and depolymerized glasses depends on the strength of OH hydrogen bonding. System confocal performance, scattering from embedding medium and glass microcrystallinity have a crucial influence on accuracy of Raman analyses of water content in glass-bearing rocks and melt inclusions in crystals.     

Pressure dependence of the speciation of dissolved water in rhyolitic melts

Water speciation in rhyolitic melts with dissolved water ranging from 0.8 to 4 wt% under high pressure was investigated. Samples were heated in a piston-cylinder apparatus at 624-1027 K and 0.94-2.83 GPa for sufficient time to equilibrate hydrous species (molecular H₂O and hydroxyl group, H₂O_m + O ? 2OH) in the melts and then quenched roughly isobarically. The concentrations of both hydrous species in the quenched glasses were measured with Fourier transform infrared (FTIR) spectroscopy. For the samples with total water content less than 2.7 wt%, the equilibrium constant (K) is independent of total H₂O concentration. Incorporating samples with higher water contents, the equilibrium constant depends on total H₂O content, and a regular solution model is used to describe the dependence. K changes with pressure nonmonotonically for samples with a given water content at a given temperature. The equilibrium constant does not change much from ambient pressure to 1 GPa, but it increases significantly from 1 to 3 GPa. In other words, more molecular H₂O reacts to form hydroxyl groups as pressure increases from 1 GPa, which is consistent with breakage of tetrahedral aluminosilicate units due to compression of the melt induced by high pressure. The effect of 1.9 GPa (from 0.94 to 2.83 GPa) on the equilibrium constant at 873 K is equivalent to a temperature effect of 49 K (from 873 K to 922 K) at 0.94 GPa. The results can be used to evaluate the role of speciation in water diffusion, to estimate the apparent equilibrium temperature, and to infer viscosity of hydrous rhyolitic melts under high pressure.     

Thermodynamic properties of anhydrous smectite MX-80, illite IMt-2 and mixed-layer illite-smectite ISCz-1 as determined by calorimetric methods. Part I: Heat capacities, heat contents and entropies

The heat capacities of the anhydrous international reference clay minerals, smectite MX-80, illite IMt-2 and mixed-layer illite-smectite ISCz-1, were measured by low temperature adiabatic calorimetry and differential scanning calorimetry, from 6 to 520 K (at 1 bar). The samples were chemically purified and Na-saturated. Dehydrated clay fractions <2 μm were studied. The structural formulae of the corresponding clay minerals, obtained after subtracting the remaining impurities, are K_0.026Na_0.435Ca_0.010(Si_3.612Al_0.388) (Al_1.593Mg_0.228Ti_0.011)O₁₀(OH)₂ for smectite MX-80, K_0.762Na_0.044(Si_3.387Al_0.613) (Al_1.427Mg_0.241O₁₀(OH)₂ for illite IMt-2 and K_0.530Na_0.135(Si_3.565Al_0.435)(Al_1.709Mg_0.218Ti_0.005)O₁₀(OH)₂for mixed-layer ISCz-1. From the heat capacity values, we determined the molar entropies, standard entropies of formation and heat contents of these minerals. The following values were obtained at 298.15 K and 1 bar:

	(J mol−1 K−1)	S0 (J mol−1 K−1)
Smectite MX-80	326.13 ± 0.10	280.56 ± 0.16
Illite IMt-2	328.21 ± 0.10	295.05 ± 0.17
Mixed-layer ISCz-1	320.79 ± 0.10	281.62 ± 0.15

Full-size table

     

Disorder and the extent of polymerization in calcium silicate and aluminosilicate glasses: O-17 NMR results and quantum chemical molecular orbital calculations

Estimation of the framework connectivity and the atomic structure of depolymerized silicate melts and glasses (NBO/T > 0) remains a difficult question in high-temperature geochemistry relevant to magmatic processes and glass science. Here, we explore the extent of disorder and the nature of polymerization in binary Ca-silicate and ternary Ca-aluminosilicate glasses with varying NBO/T (from 0 to 2.67) using O-17 NMR at two different magnetic fields of 9.4 and 14.1 T in conjunction with quantum chemical calculations. Non-random distributions among framework cations (Si and Al) are demonstrated in the variation of relative populations of oxygen sites with NBO/T. The proportion of non-bridging oxygen (NBO, Ca-O-Si) in the binary and ternary aluminosilicate glasses increases with NBO/T. While the trend is consistent with predictions from composition, the detailed fractions apparently deviate from the predicted values, suggesting further complications in the nature of polymerization. The proportion of each bridging oxygen in the glasses also varies with NBO/T. The fractions of Al-O-Si and Al-O-Al increase with increasing polymerization as CaO is replaced with Al₂O₃, while that of Si-O-Si seems to decrease, implying that activity of silica may decrease from calcium silicate to polymerized aluminosilicates (X_SiO2=constant). Quantum chemical molecular orbital calculations based on density functional theory show that a silicate chain with Al-NBO (Ca-O-Al) has an energy penalty (calculated cluster energy difference) of about 108 kJ/mol compared with the cluster with Ca-O-Si, consistent with preferential depolymerization of Si-networks, reported in an earlier O-17 NMR study [Allwardt, J., Lee, S.K., Stebbins, J.F., 2003. Bonding preferences of non-bridging oxygens in calcium aluminosilicate glass: Evidence from O-17 MAS and 3QMAS NMR on calcium aluminate glass. Am. Mineral.88, 949-954]. These prominent types of non-randomness in the distributions suggest significant chemical order in silicate glasses that leads to a decrease in silica activity coefficient and will be useful in modeling transport properties of melts.