Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy

The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [^[4]B; natural danburite (CaB₂Si₂O₈) and synthetic boron phosphate (BPO₄)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of ^[4]B sites to ^[3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials. Received: 7 April 1997 / Accepted: 30 July 1997     

Two-liquid partition coefficients: Experimental data and geochemical implications

Partition coefficients for Cs, Ba, Sr, Ca, Mg, La, Sm, Lu, Mn, Ti, Cr, Ta, Zr, and P between immiscible basic and acidic liquids in the system K₂O-Al₂O₃-FeO-SiO₂ were experimentally determined at 1,180 °C and 1 atm. Phosphorus is most strongly enriched in the basic melt (by a factor of 10), followed by rare earth elements, Ta, Ca, Cr, Ti, Mn, Zr, Mg, Sr, and Ba (enriched by a factor of 1.5). Of the elements studied, only Cs is enriched in the acidic melt. The two-liquid partition coefficients of Zr, Ta, Sm, and Mn are constant for concentrations ranging from <0.1% to as high as 1 wt.-%, suggesting that Henry's law is applicable in silicate melts (at least for these elements) to concentrations well above typical trace element levels in rocks. The strong relative preference of many elements for the basic melt implies that the structural characteristics of basic melts more readily permit stable coordination of cations by oxygen. Partitioning of elements between crystal and liquid in a magma must therefore be influenced by the composition (and consequent structure) of the liquid.Application of the two-liquid partition coefficients to possible occurrences of liquid immiscibility in magmas reveals that typical basalt-rhyolite associations are probably not generated by two-liquid phase separation. However, liquid immiscibility cannot be discounted as a possible origin for lamprophyric rocks containing felsic segregations.     

Experiments on liquid immiscibility along tholeiitic liquid lines of descent

Crystallization experiments have been conducted on compositions along tholeiitic liquid lines of descent to define the compositional space for the development of silicate liquid immiscibility. Starting materials have 46–56 wt% SiO₂, 11.7–17.7 wt% FeO_tot, and Mg-number between 0.29 and 0.36. These melts fall on the basaltic trends relevant for Mull, Iceland, Snake River Plain lavas and for the Sept Iles layered intrusion, where large-scale liquid immiscibility has been recognized. At one atmosphere under anhydrous conditions, immiscibility develops below 1,000–1,020°C in all of these compositionally diverse lavas. Extreme iron enrichment is not necessary; immiscibility also develops during iron depletion and silica enrichment. Variations in melt composition control the development of silicate liquid immiscibility along the tholeiitic trend. Elevation of Na₂O + K₂O + P₂O₅ + TiO₂ promotes the development of two immiscible liquids. Increasing melt CaO and Al₂O₃ stabilizes a single-liquid field. New data and published phase equilibria show that anhydrous, low-pressure fractional crystallization is the most favorable condition for unmixing during differentiation. Pressure inhibits immiscibility because it expands the stability field of high-Ca clinopyroxene, which reduces the proportion of plagioclase in the crystallizing assemblage, thus enhancing early iron depletion. Magma mixing between primitive basalt and Fe–Ti–P-rich ferrobasalts can serve to elevate phosphorous and alkali contents and thereby promote unmixing. Water might decrease the temperature and size of the two-liquid field, potentially shifting the binodal (solvus) below the liquidus, leading the system to evolve as a single-melt phase.     

An experimental study of the effect of boron on a water saturated haplogranite at 1 Kbar vapour pressure

An experimental study of the effect of boron in the water saturated Q-Or-Ab-B₂O₃-H₂O system has been performed at P=1 Kbar to provide experimental data and explain the role of boron in some late magmatic and early hydrothermal events. Experiments were conducted between 500° C and 800° starting from a gel, or a previously crystallized gel, and variable amounts of boron (0 to 18% B₂O₃) added to water. The phases obtained were: quartz, sanidine, albite, silicate liquid quenched to glass, and aqueous vapour phase. Boric acids, borates and isotropic low index materials were found in the quenched vapour phase. An aluminium silicate-like mineral, not yet fully identified, is also present.The solidus temperature of the Q-Or-Ab composition is lowered by 60° C when 5 wt. % B₂O₃ is added and by more than 130° C when 17wt. % B₂O₃ is added. Compositions of equilibrated silicate melts and vapours were obtained between 780° C and 750° C for various B₂O₃ concentrations. The vapour phase is B and Si rich. It is also enriched in Na with respect to K, and in alkalis with respect to Al. Its silicate solute content is higher than in experiments with pure water. The solubility of water is increased by the addition of boron in Q-Or-Ab melts. Microprobe data show that the melts equilibrated with vapour phases become hyperaluminous and more potassic than sodic. The partition coefficient of boron is in favour of the vapour (k _D=B₂O₃% in melt/B₂O₃% in vapour=0.33±0.02). The effect of the interaction between the silicate phases and the vapour is discussed. Comparison is made between the behaviour of boron and that of chlorine and fluorine. Geological applications are also provided, which concern the influence of boron on minimum melting, on muscovite stability and on the hypersolvus-subsolvus transition.     

Thermochemical study of glasses in the system CaMgSi2O6-CaAl2SiO6

High temperature solution calorimetry of glasses in the system CaMgSi₂O₆ (Di)-CaAl₂SiO₆ (CaTs) show them to have negative enthalpies of mixing with a regular enthalpy parameter, W_H, of -11.4 ± 0.7 kcal. Negative heats of mixing between alumina-rich and alumina-poor glasses seem to be a general phenomenon in aluminosilicates and are not confined only to glassy systems containing anorthite as a component. The thermodynamic behavior of glasses in the system SiO₂-Ca_0.5;AlO₂-CaMgO₂ appears to vary in a smooth fashion, with small positive heats of mixing near SiO₂ and substantial negative heats of mixing for other compositions. The exothermic behavior with increasing $\text{A1}\text{(Al + Si)}$ may be related to local charge balance of M²⁺ and Al³⁺. The negative heats of mixing in MgCaSi₂O₆-CaAl₂SiO₆, MgCaSi₂O₆-CaAl₂Si₂O₈ and NaAlSi₃O₈-CaAl₂Si₂O₈ glasses are in contrast to the positive heats of mixing found in MgCaSi₂O₆-CaAl₂SiO₆ (pyroxene) and NaAlSi₃O₈-CaAl₂Si₂O₈ (high plagioclase) crystalline solid solutions.     

Thermochemical study of glasses in the system NaAlSi3O8-KAlSi3O8-Si4O8 and the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8

Enthalpies of solution in 2PbO · B₂O₃ at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na_1.6Al_1.6Si_2.4O₈-K_1.6Al_1.6Si_2.4O₈. The join KAlSi₃O₈-Si₄O₈ shows zero heat of mixing similar to that found previously for NaAlSi₃O₈-Si₄O₈ glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab₅₀Or₅₀ (W_n = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at $\text{Si}\text{(Si + Al)}\text{= 0.6.}$ Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol^?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO₂.     

Transport properties of high albite crystals,near-endmember feldspar and pyroxene glasses,and their melts to high temperature

Thermal diffusivity (D) was measured using laser-flash analysis (LFA) from oriented single-crystal albite and glasses near LiAlSi₃O₈, NaAlSi₃O₈, CaAl₂Si₂O₈, LiAlSi₂O₆ and CaMgSi₂O₆ compositions. Viscosity measurements of the supercooled liquids, over 2.6 × 10⁸ to 8.9 × 10¹² Pa s, confirm strongly non-Arrhenian behavior for CaAl₂Si₂O₈, and CaMgSi₂O₆, and near-Arrhenian behavior for the others. As T increases, D _glass decreases, approaching a constant near 1,000 K. Upon crossing the glass transition, D decreases rapidly. For feldspars, D for the melt is ~15% below D of the bulk crystal, whereas for pyroxenes, this difference is ~40%. Thermal conductivity (k _lat = ρC _P D) of crystals decreases with increasing T, but k _lat of glasses increases with T because heat capacity (C _P ) increases with T more strongly than density (ρ) and D decrease. For feldspars, k _lat for the melt is ~10% below that of the bulk crystal or glass, whereas this decrease for pyroxene is ~50%. Therefore, melting substantially impedes heat transport, providing positive thermal feedback that could promote further melting.     

Measurement of the effects of temperature and partial pressure of oxygen on the oxidation states of europium in silicate glasses

The techniques of electron paramagnetic resonance (EPR) were used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in quenched CaMgSi₂O₆, Ca₃Si₃O₁₂, and CaAl₂Si₂O₈ liquids as functions of partial pressure of oxygen and temperature. The redox equilibrium of the Eu ions was described by the reaction 4Eu³⁺ + 20^2? = 4Eu²⁺ + O₂. The reduction of Eu³⁺ to Eu²⁺ was endothermic, and for CaMgSi₂O₆ and Ca₃Al₂Si₃O₁₂ liquids the mean value of ΔH⁰ and the standard deviation from that mean were 25 ± 7 kcal/mole.The magnitude of the Eu anomaly in the distribution coefficients is discussed in terms of the compositions of the solid and liquid phases.     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

Thermodynamic analysis of Fe and Mg partitioning between plagioclase and silicate liquid

 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl₂Si₂O₈-CaFeSi₃O₈ and CaAl₂Si₂O₈-CaMgSi₃O₈. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe³⁺ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe³⁺/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X _Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X _Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999     

Dynamics of Na in sodium aluminosilicate glasses and liquids

²³Na NMR measurements on Na₂Si₃O₇, Na₃AlSi₆O₁₅, and NaAlSi₃O₈ glasses from room temperature to 1200°C show that the dynamics and local structure of sodium in silicate/aluminosilicate glasses and melts vary with composition and temperature.The peak positions decrease in frequency between room temperature and 200°C indicating that the Na sees a larger average site as temperature is increased. Between 200°–300° and 700°C, line widths, nutation frequencies and peak positions are consistent with motional averaging of quadrupolar satellites. Above 700°C there is little or no change in the peak positions with temperature. Chemical shifts of the materials at 1000°C (Na₂Si₃O₇: 3.6; Na₃AlSi₆O₁₅:-1.3; NaAlSi₃O₈:-6.4 ppm) indicate a slight change in the average Na coordination number from 6–7 for the silicate to 7–8 for the aluminosilicates.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—V. The polymeric structure of silica in albite and anorthite composition glass and the devitrification of amorphous anorthite

²⁹Si MAS NMR experiments have been carried out to determine the silica species distribution (Q distribution) in albite, NaAlSi₃O₈, and anorthite, CaAl₂Si₂O₈, composition glasses (designated albite and anorthite glass). Our results indicate that the Q distribution of albite glass contains all five possible silica species and shows a tendency towards high Q₃ and Q₄ concentrations, whereas anorthite glass does not contain Q₄ and has a high Q₀ concentration. Rationalizations are made in terms of the observed Q distributions to explain differences in devitrification behavior of these two glasses. ²⁷Al MAS NMR data for these glasses suggest that differences in devitrification behavior between these two glasses should be ascribed to small growth rates rather than small nucleation rates of crystalline albite from albite glass.     

The role of liquid immiscibility in the genesis of carbonatites — An experimental study

The two-liquid field between alkali-carbonate liquids and phonolite or nephelinite magmas from the Oldoinyo Lengai volcano has been determined between 0.7 and 7.6 kb and 900°–1,250° C. The miscibility gap expands with increase in and decrease in temperature. Concomitantly there is a rotation of tie-lines so that the carbonate liquids become richer in CaO. The element distribution between the melts indicates that a carbonate liquid equivalent in composition to Oldoinyo Lengai natrocarbonatite lava would have separated from a phonolitic rather than a nephelinitic magma. CO₂-saturated nephelinites coexist with carbonate liquids much richer in CaO than the Lengai carbonatites, but even so these liquids have high alkali concentrations. If the sövites of hypabyssal and plutonic ijolite-carbonatite complexes originated by liquid immiscibility, then large quantities of alkalis have been lost, as is suggested by fenitization and related phenomena. The miscibility gap closes away from Na₂O-rich compositions, so that the tendency to exsolve a carbonatite melt is greater in salic than in mafic silicate magmas. The two-liquid field does not approach kimberlitic compositions over the range of pressures studied, suggesting that the globular textures observed in many kimberlite sills and dykes may be the result of processes other than liquid immiscibility at crustal pressures.     

High temperature heat contents and heat capacities of liquids and glasses in the system NaAlSi3O8-CaAl2Si2O8

Enthalpies and heat capacities of glasses and of stable liquids in the system NaAlSi₃O₈-CaAl₂Si₂O₈ have been measured by drop and differential scanning calorimetry. Within experimental error, values of C _p and of H _{T 300} of three intermediate compositions fall on straight line interpolations between the end members for both liquids and glasses, indicating that excesses in true and in mean heat capacities [(H _T –H ₃₀₀)/(T–300)] are small or absent. A value for the heat capacity of the An₁₀₀ liquid component can therefore be derived, and is probably a better estimate than that based on measurements on the pure substance alone. On the assumption of zero excess heat capacity in this system, heats of mixing in the stable liquids are equal to those measured in the glasses by solution calorimetry, and can be as negative as -2 kcal mol^–1.Heat capacities of solids and glasses in the Ab-An system are similar and do not vary greatly with composition. The C _P's of the liquids, however, increase strongly with An content, suggesting major structural changes take place across the binary.     

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl₂Si₂O₈; denoted AN), albite (NaAlSi₃O₈; denoted AB), and diopside (CaMgSi₂O₆; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D_Ca/D_Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D_Ca/D_Si ≈ 1. In the AB-DI experiment, D_Ca/D_Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D_Mg/D_Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids.The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation (D_Ca) to the diffusivity of silicon (D_Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D_cation/D_Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and D_cation/D_H2O, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.     

Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts

The coordination environment of Fe(II) has been examined in seven anhydrous ferrosilicate glasses at 298 K and 1 bar using ⁵⁷Fe Mössbauer, Fe K-edge X-ray near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), UV-Vis-NIR, and magnetic circular dichroism (MCD) spectroscopies. Glasses of the following compositions were synthesized from oxide melts (abbreviation and nonbridging oxygen:tetrahedral cation ratio (NBO/T) in parentheses): Li₂FeSi₃O₈ (LI2: 1.33), Rb₂FeSi₃O₈ (RB2: 1.33), Na_l.08Fe_l.l7Si_3.l3O₈ (NAl: 1.09), Na_l.46Ca_0.24Fe_l.08Si_2.97O₈ (NC6: 1.38), Na_l.09Ca_0.51Fe_0.72Si_3.10O₈ (NC2: 1.15), Na_0.99Ca_0.92Fe_0.24 Si_3.17O₈ (NCl: 1.04), and Na_0.29Mg_0.53Ca_0.52Fe_0.56Al_0.91Si_2.44O₈ (BAS: 1.05). Mössbauer, XANES, and EXAFS information suggests that iron is dominantly ferrous in all glasses (<10 atom% Fe(III)) with an average first-neighbor Fe(II) coordination varying from ∼ 4 to 5.2 (±0.2) oxygens. The UV-Vis-NIR spectrum of each sample exhibits intense absorption centered near 8100-9200 cm⁻¹ and weak absorption near 5000 cm^−l, which cannot be assigned unambiguously. The MCD spectrum of NC6 glass, which is the first such measurement on a silicate glass, shows three transitions at ∼8500 cm⁻¹, ∼6700 cm⁻¹, and ∼4500 cm⁻¹. The behavior of these MCD bands as a function of temperature (1.6 K to 300 K) and magnetic field strength (1 T to 7 T) indicates that they most likely arise from three distinct Fe(II) sites with different ground states, two of which are 5-coordinated and one of which is 4-coordinated by oxygens.The combined results suggest that Fe(II) predominantly occupies 5- and 4-coordinated sites in each glass, with the ratios differing for the different compositions. Small amounts of 6-coordinated Fe(II) are possible as well, but primarily in the more basic glass compositions such as BAS. The substitution of Li(I) for Rb(I) in the M₂FeSi₃O₈ base glass composition causes a weakening of the average Fe(II)-O bond, as indicated by the longer Fe(II)-O distance in the latter. The basalt composition glass was found to have the largest Fe(II) sites relative to those in the other glasses in this study. A bond valence model that helps predict the coordination number of Fe(II) in silicate glasses is proposed. The structural information extrapolated to Fe(II)-bearing melts is parameterized using bond valence theory, which helps to rationalize the melt-crystal partitioning behavior of ferrous iron in natural and synthetic melt-crystal systems.     

Thermochemistry of glasses along joins of pyroxene stoichiometry in the system Ca2Si2O6-Mg2Si2O6-Al4O6

Enthalpies of solution in 2PbO · B₂O₃ at 974 K have been measured for glasses along the joins Ca₂Si₂O₆ (Wo)-Mg₂Si₂O₆ (En) and Mg₂Si₂O₆-MgAl₂SiO₆ (MgTs). Heats of mixing are symmetric and negative for Wo-En with W_H = ?31.0 ± 3.6 kJ mol^?. Negative heats of mixing were also found for the En-MgTs glasses (W_H = ?33.4 ± 3.7 kJ mol^?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested.     

Structure-composition relations and Raman spectroscopy of high-pressure sodium silicates

?-Na₂Si₂O₅, ζ-Na₂Si₂O₅, Na₂Si[Si₂O₇], and Na₆Si₃[Si₉O₂₇] have been synthesized using an MA6/8 superpress. Densification in high-pressure sodium silicates is effected largely by changes in packing. In the relaxed (1 bar) structures, cation polyhedra and thermal/displacement parameters are similar to those of low-pressure silicates, but the extra-framework cation positions are oversized. The two mixed ^[4]Si and ^[6]Si framework silicates of known structure (Na₂Si[Si₂O₇] and Na₆Si₃[Si₉O₂₇]) belong to the limited homologous series Na_2mSi_m[Si_n–mO_2n+m], with m<n. The structure-composition relationships of wadeite-type, A₂Ge₄O₉-type, and Na₆Si₃[Si₉O₂₇] silicates and germanates depend on T-O distance and size of the large extra-framework cation. Characteristic features of the SiO₄ tetrahedral units are present in micro-Raman spectra of mixed ^[4]Si and ^[6]Si framework silicates, but bands uniquely attributable to SiO₆ octahedra are weak or obscured. However, ^[6]Si has a profound indirect influence on the Raman spectra, resulting in intense and complex low-frequency bands, assigned to symmetric bending modes with coupled displacements at both bridging oxygens and nonbridging oxygens bonded to ^[6]Si, and a shift to higher frequency and reduction in intensity of the high-frequency bands assigned to symmetric ^[4]Si-O_nbr stretching vibrations. Raman spectroscopy does not appear to be a useful structural probe for small amounts of ^[6]Si in silicate glasses and melts.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

Thermochemistry of glasses and liquids in the systems CaMgSi2O6-CaAl2Si2O8-NaAlSi3O8, SiO2-CaAl2Si2O8-NaAlSi3O8 and SiO2-Al2O3-CaO-Na2O

Enthalpies of solution in 2PbO· B₂O₃ at 712°C have been measured for glasses in the systems albite anorthite diopside, NaAlO₂-SiO₂, Ca_0.5AlO₂-SiO₂ and albite-anorthite-quartz. The systems albite-anorthite and diopside-anorthite show substantial negative enthalpies of mixing, albite-diopside shows significant positive heats of mixing. For compositions up to NaAlO₂ = 0.42 (which includes the subsystem albite-silica) the system NaAlO₂-SiO₂ shows essentially zero heats of mixing. A negative ternary excess heat of mixing is found in the plagioclase-rich portion of the albite-anorthite-diopside system. The join Si₄O₈-CaAl₂Si₂O₈ shows small but significant heats of mixing. In albite-anorthite-quartz. ternary glasses, the ternary excess enthalpy of mixing is positive.Based on available heat capacity data and appropriate consideration of the glass transition, the enthalpy of the crystal-glass transition (vitrification) is a serious underestimate of the enthalpy of the crystal-liquid transition (fusion) especially when the melting point, T_f, is many hundreds of degrees higher than the glass transition temperature, T_g. On the other hand, the same heat capacity data suggest that the enthalpies of mixing in albite-anorthite-diopside liquids are calculated to be quite similar to those in the glasses. The enthalpies of mixing observed in general support the structural models proposed by Taylor and Brown (1979a, b) and others for the structure of aluminosilicate glasses.