A computer simulation study of natural silicate melts. Part I: Low pressure properties

In implementing into a molecular dynamics simulation code a simple interionic potential developed to describe the nine component system K₂O-Na₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ (KNCMFATS), it has been possible to reproduce satisfactorily a number of thermodynamic, structural and transport properties of a representative set of natural silicate melts. An important conclusion reached in this study is the good transferability of the potential from felsic to ultramafic compositions although this transferability becomes less accurate with high silica contents (rhyolitic composition and beyond) and with very iron-rich silicates (e.g. fayalite). A key feature of the simulation is to make the link between macroscopic properties of the melt and its microscopic structure and dynamics. We thus obtain a relationship between the molar volume of the melt, the number of network modifiers and the oxygen coordination number. The simulation also allows one to quantify the coordination environment around the cations as function of the melt composition. Furthermore, the electrical conductivity of the high temperature liquid is investigated.     

Carbon dioxide in silicate melts: A molecular dynamics simulation study

We have performed a series of molecular dynamics simulations aimed at the evaluation of the solubility of CO₂ in silicate melts of natural composition (from felsic to ultramafic). In making in contact within the simulation cell a supercritical CO₂ phase with a silicate melt of a given composition, we have been able to evaluate (i) the solubility of CO₂ in the P-T range 1473-2273 K and 20-150 kbar, (ii) the density change experienced by the CO₂-bearing melt, (iii) the respective concentrations of CO₂ and species in the melt, (iv) the lifetime and the diffusivity of these species and (v) the structure of the melt around the carbonate groups. The main results are the following:(1) The solubility of CO₂ increases markedly with the pressure in the three investigated melts (a rhyolite, a mid-ocean ridge basalt and a kimberlite) from about ∼2 wt% CO₂ at 20 kbar to ∼25 wt% at 100 kbar and 2273 K. The solubility is found to be weakly dependent on the melt composition (as far as the present compositions are concerned) and it is only at very high pressure (above ∼100 kbar) that a clear hierarchy between solubilities occurs (rhyolite < MORB < kimberlite). Furthermore at a given pressure the calculated solubility is negatively correlated with the temperature.(2) In CO₂-saturated melts, the proportion of carbonate ions is positively correlated with the pressure at isothermal condition and is negatively correlated with the temperature at isobaric condition (and vice versa for molecular CO₂). Furthermore, at fixed (P, T) conditions the proportion of carbonate ions is higher in CO₂-undersaturated melts than in the CO₂-saturated melt. Although the proportion of molecular CO₂ decreases when the degree of depolymerization of the melt increases, it is still significant in CO₂-saturated basic and ultrabasic compositions at high temperatures. This finding is at variance with experimental data on CO₂-bearing glasses which show no evidence of molecular CO₂ as soon as the degree of depolymerization of the melt is high (e.g. basalt). These conflicting results can be reconciled with each other by noticing that a simple low temperature extrapolation of the simulation data predicts that the proportion of molecular CO₂ in basaltic melts might be negligible in the glass at room temperature.(3) The carbonate ions are found to be transient species in the liquid phase, with a lifetime increasing exponentially with the inverse of the temperature. Contrarily to a usual assumption, the diffusivity of carbonate ions into the liquid silicate is not vanishingly small with respect to that of CO₂ molecules: in MORB they differ from each other by a factor of ∼6 at 1473 K and only a factor of ∼2 at 2273 K. Although the bulk diffusivity of CO₂ is governed primarily by the diffusivity of CO₂ molecules, the carbonate ions contribute significantly to the diffusivity of CO₂ in depolymerized melts.(4) Concerning the structure of the CO₂-bearing silicate melt, the carbonate ions are found to be preferentially associated with NBO’s of the melt, with an affinity for NBOs which exceeds that for BOs by almost one order of magnitude. This result explains why the concentration in carbonate ions is positively correlated with the degree of depolymerization of the melt and diminishes drastically in fully polymerized melts where the number of NBO’s is close to zero. Furthermore, the network modifier cations are not randomly distributed in the close vicinity of carbonate groups but exhibit a preferential ordering which depends at once on the nature of the cation and on the melt composition. However at the high temperatures investigated here, there is no evidence of long lived complexes between carbonate groups and metal cations.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

Isovalent trace element partitioning between minerals and melts: A computer simulation study

We present a new approach for the rationalisation of trace element partitioning between silicate melts and minerals, which is not based on the empirical, parameterised continuum models in common use. We calculate the energetics of ion substitution using atomistic simulation techniques, which include an explicit evaluation of the relaxation energy (strain energy) contribution to this process. Solution energies are estimated for isovalent impurities in CaO, diopside, orthoenstatite, and forsterite. These show a parabolic dependence on ionic radius, similar to the variation of mineral-melt partition coefficients with ionic radius. The success of the empirical models, which often include only the strain energy, appear to have been due to the partial cancellation of energy terms, and to the empirical fitting of the parameters included in these models. Our approach can be readily extended to aliovalent substitution.     

Nature of polymerization and properties of silicate melts and glasses at high pressure

The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [¹⁷O and ²⁷Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as ^[4]Al, ^[5,6]Al, ^[4]Si, and ^[5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as ^[4]Si-O-^[5,6]Si, ^[4]Si-O-^[5,6]Al and Na-O-^[5,6]Si. While the fractions of ^[5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O²⁻ diffusivity and viscosity often observed in silicate melts.     

Iron-bearing silicate melts: Relations between pressure and redox equilibria

Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na₂Si₂O₅-Fe₂O₃ to 40 kbar pressure at 1400° C. The Fe³⁺/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe³⁺ to Fe²⁺ and coordination transformation of remaining Fe³⁺ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.     

Dual speciation of nitrogen in silicate melts at high pressure and temperature: An experimental study

Solubility and speciation of nitrogen in silicate melts have been investigated between 1400 and 1700 °C and at pressures ranging from 10 to 30 kbar for six different binary alkali and alkaline-earth silicate liquids and a Ca-Mg-alumino silicate. Experiments were performed in a piston-cylinder apparatus. The nitrogen source is silver azide, which breaks down to Ag and molecular N₂ below 300 °C. At high pressure and temperature, the nitrogen content may be as high as 0.7 wt% depending on the melt composition, pressure, and temperature. It increases with T, P and the polymerization state of the liquid. Characterization by Raman spectroscopy and ¹⁵N solid state MAS NMR indicates that nitrogen is not only physically dissolved as N₂ within the melt structure like noble gases, but a fraction of nitrogen interacts strongly with the silicate network. The most likely nitrogen-bearing species that can account for Raman and NMR results is nitrosyl group. Solubility data follow an apparent Henry’s law behavior and are in good agreement with previous studies when the nitrosyl content is low. On the other hand, a significant departure from a Henry’s law behavior is observed for highly depolymerized melts, which contain more nitrosyl than polymerized melts. Possible solubility mechanisms are also discussed. Finally, a multi-variant empirical relation is given to predict the relative content of nitrosyl and molecular nitrogen as a function of P, T, and melt composition and structure. This complex speciation of nitrogen in melts under high pressure may have significant implication concerning crystal-melt partitioning of nitrogen as well as for potential elemental and isotopic fractionation of nitrogen in the deep Earth.     

Structure of silicate melts: Raman spectroscopic data and thermodynamic simulation results

High-temperature Raman spectroscopy was applied to study model silicate melts in the M₂O-SiO₂ system, where M = K, Na, or Li. Structural units of the melts and equilibrium constants of reactions between them are determined. Thermodynamic calculations were conducted for the dependence of the Q ⁿ distribution on the composition and temperature, and the results of thermodynamic simulations were demonstrated to be consistent with the experimental results.     

Structural controls and mechanisms of diffusion in natural silicate melts

The diffusion properties of Na, Cs, Ba, Fe and Eu ions have been determined experimentally for a pantellerite melt and of these ions plus Li, Mn and Co in pitchstone melt, using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,200–1,400° C. In addition, Eu diffusion in a basaltic and an andesitic melt was determined. Diffusion of all cations follows an Arrhenius relationship, activation energy values being high for diffusion in the pantellerite melt (e.g. Eu: 100 kcal mol^–1) except in the case of Na (24.3 kcal mol^–1). Activation energies of diffusion in the pitchstone melt are similar to values recorded earlier for andesitic and basaltic melts.The new data are used, along with previously published data for diffusion in other composition melts, to examine the compositional and structural controls on diffusion. The range of diffusivities shows a marked change with melt composition; over two orders of magnitude for a basaltic melt, and nearly four orders for a pantellerite melt (both at 1,300° C). Diffusivity of all cations (except Li and Na) correlates positively with the proportion of network modifying cations. In the case of Li and Na the correlation is negative but the diffusivity of these ions correlates positively with the proportion of Na or of Na + K ions in the bulk melt. Diffusion behaviour in the pantellerite melt departs from the relationships shown by the data for other melt compositions, which could be partly explained by trivalent ions (such as Fe) occupying network forming positions. The diffusivity of alkali metal ions is strongly dependent on ionic radius, but this is not the case with the divalent and trivalent ions; diffusivity of these ions remains relatively constant with change in radius but decreases with increase in ionic charge.A compensation diagram shows four distinct but parallel trends for the majority of the cations in four melt types but the data for Li and Na plot on a separate trend. This and the other relationships are used to elucidate possible mechanisms of diffusion. Exchange mechanisms appear to be common, with the preservation of local charge balance. Li and Na diffuse by a distinct mechanism which involves exchange of similar or identical ions. The diffusion behaviour of the smaller alkali metal ions is sufficiently distinct from all other cations to indicate that diffusion could be an important factor in the geochemical fractionation of the alkali elements.s     

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.     

High pressure polymorphism of dicalcium silicate Ca2SiO4. A transmission electron microscopy study

Ca₂SiO₄ dicalcium silicate has been transformed at high pressure in a diamond-anvil cell (DAC) coupled with a YAG laser heater, in order to study the high-pressure modifications of this compound. Starting material was the olivine form of Ca₂SiO₄ (γ-polymorph). Several samples have been synthesized at loading pressures of 4.5, 10 and 15 GPa respectively, at room temperature. Other samples have been obtained at pressures ranging between 4.5 and 45 GPa and temperatures estimated to be about 2500 °C. The study of the quenched high pressure and/or high temperature phases has been performed using analytical transmission electron microscopy (ATEM) and X-ray diffraction (XRD). All the polymorphs of Ca₂SiO₄ usually produced with high temperatures, including α-Ca₂SiO₄, have been observed in the samples recovered from the high-pressure experiments. The α′-Ca₂SiO₄ and α-Ca₂SiO₄ polymorphs have been obtained at ambient conditions for the first time without stabilizing impurities. A new modification of α′-Ca₂SiO₄ has also been synthesized. Finally, the breakdown at high-pressure and temperature of Ca₂SiO₄ into CaSiO₃ and CaO is reported.     

Infrared spectroscopic study of the silicate anionic structures of some magmatic silicate melts

Summary The relation between the species of silicate anions in a silicate melt and their infrared characteristic frequency is discussed. A simple relation approximated with a quadratic equation is established between the ratio of non-bridging oxygens to silicon atoms of a silicate anion and the characteristic frequency. Based on this relation, the silicate anions in some magmatic silicate melts were estimated. The results obtained in the present study agreed well qualitatively with those estimated by some researchers on the basis of other spectroscopic methods.The constituent silicate segments and the distribution of AlO₄ tetrahedra in fully polymerized melts, albite, jadeite and anorthite, have been investigated. The polymerization degree of the silicate segments in the network seemed to decrease with the increase of AlO₄ tetrahedron. It is also suggested, that AlO₄ in the albite melt distributed more randomly, while those in anorthite melt had a tendency to form an aluminous segment.

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Infrarot-spektroskopische Untersuchungen der Silikatanionen-Strukturen einiger magmatischer Silikatschmelzen

Zusammenfassung Die Beziehungen zwischen den Spezies der Silikatanionen in den Silikatschmelzen und ihrer charakteristischen Infrarot-Frequenz wurde untersucht. Es gibt eine einfache Beziehung zwischen dem Verhältnis nicht brückenbildender Sauerstoffatome zu Si-Atomen der Silikatanionen und der charakteristischen Frequenz, die mit einer quadratischen Gleichung beschrieben werden kann. Auf Grund dieser Beziehung werden die Silikatanionen in einigen magmatischen Schmelzen abgeschätzt. Das Ergebnis dieser Untersuchung stimmt qualitativ mit den Werten überein, die von einigen Forschern durch andere spektroskopische Methoden erhalten wurden.Die Silikatsegmente und die Verteilung der AlO₄-Tetraeder in vollkommen polymerisierten Schmelzen, in Albit, Jadeit und Anorthit wurden untersucht. Der Polymerisationsgrad der Silikatsegmente in den Netzwerken scheint mit der Zunahme der AlO₄-Tetraeder geringer zu werden. Die Untersuchungläßt erkennen, daß AlO₄-Tetraeder in Albit unregelmäßig verteilt sind, und in Anorthit die Neigung haben, ein Al-Segment zu bilden.

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With 6 Figures     

Dehydration melting of tonalites. Part II. Composition of melts and solids

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996     

Microscopic origins of macroscopic properties of silicate melts and glasses at ambient and high pressure: Implications for melt generation and dynamics

Recent development and advances in solid state NMR, together with theoretical analyses using quantum-chemical calculations and statistical mechanical modeling, have allowed us to estimate and quantify the detailed distributions of cations and anions in model silicate glasses and melts with varying pressure, temperature and composition. How these microscopic, atomic-scale distributions in the melts from NMR and simulations affect the thermodynamic and transport properties relevant to magmatic processes has been extensively explored recently. Here, based on these previous studies, we present a classification scheme to quantify the various aspects of disorder in covalent oxide glasses and melts on scales of less than 1 nm. The scheme includes contributions from both chemical and topological disorder. Chemical disorder can further be divided into [1] connectivity, which quantifies the extent of mixing among framework units (often parameterized by the degree of Al avoidance or phase separation) and the extent of polymerization (mixing between framework and nonframework cations), and [2] nonframework disorder, which denotes the distribution of network-modifying or charge-balancing cations. Topological disorder includes the distribution of bond lengths and angles. We use this framework of disorder quantification to summarize recent progress on the structures of silicate melts and glasses, mainly obtained from 2D triple quantum magic-angle spinning (3QMAS) NMR, as functions of temperature, pressure, and composition.Most glasses and melts studied show a tendency for chemical ordering in connectivity, nonframework disorder and topological disorder at ambient and high pressure. The chemical ordering in framework disorder, a manifestation of energetics in the melts and glasses, contributes to the total negative deviation of activity of oxides from ideal solution in silicate melts (reduced activity). While no definite evidence of clustering among nonframework cations was found, these cations tend to form dissimilar pairs upon mixing with other types of network modifying cations. Topological disorder in silicate glasses and melts tends to increase with increasing pressure, as suggested by increasing bond angle and length distribution, while the chemical order seems to be maintained with pressure. We calculate key macroscopic properties, including the activity coefficient of silica and viscosity, based on the quantitative estimation of the extent of disorder from solid-state NMR, in particular ¹⁷O 3QMAS NMR. Structural ordering in melts may strongly affect the composition of partial melts in equilibrium with solids, increasing the silica composition of partial melts as a result. With increasing chemical order, the configurational entropy decreases, which can be correlated to an increase in viscosity of melts.     

Partial melting of metagreywackes, Part II. Compositions of minerals and melts

A series of experiments on the fluid-absent melting of a quartz-rich aluminous metagreywacke has been carried out. In this paper, we report the chemical composition of the phases present in the experimental charges as determined by electron microprobe. This analytical work includes biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100–1000 MPa, 780–1025 °C. Biotites are Na- and Mg-rich, with Ti contents increasing with temperature. The compositions of plagioclase range from An₁₇ to An₃₅, with a significant orthoclase component, and are always different from the starting minerals. At high temperature, plagioclase crystals correspond to ternary feldspars with Or contents in the range 11–20 mol%. Garnets are almandine pyrope grossular spessartine solid solutions, with a regular and significant increase of the grossular content with pressure. All glasses are silicic (SiO₂ = 67.6–74.4 wt%), peraluminous, and leucocratic (FeO + MgO = 0.9–2.9 wt%), with a bulk composition close to that of peraluminous leucogranites, even for degrees of melting as high as 60 vol.%. With increasing pressure, SiO₂ contents decrease while K₂O increases. At any pressure, the melt compositions are more potassic than the water-saturated granitic minima. The H₂O contents estimated by mass balance are in the range 2.5–5.6 wt%. These values are higher than those predicted by thermodynamic models. Modal compositions were estimated by mass balance calculations and by image processing of the SEM photographs. The positions of the 20 to 70% isotects (curves of equal proportion of melt) have been located in the pressure-temperature space between 100 MPa and 1000 MPa. With increasing pressure, the isotects shift toward lower temperature between 100 and 200 MPa, then bend back toward higher temperature. The melting interval increases with pressure; the difference in temperature between the 20% and the 70% isotects is 40 °C at 100 MPa, and 150 °C at 800 MPa. The position of the isotects is interpreted in terms of both the solubility of water in the melt and the nature of the reactions involved in the melting process. A comparison with other partial melting experiments suggests that pelites are the most fertile source rocks above 800 MPa. The difference in fertility between pelites and greywackes decreases with decreasing pressure. A review of the glass compositions obtained in experimental studies demonstrates that partial melting of fertile rock types in the crust (greywackes, pelites, or orthogneisses) produces only peraluminous leucogranites. More mafic granitic compositions such as the various types of calk-alkaline rocks, or mafic S-type rocks, have never been obtained during partial melting experiments. Thus, only peraluminous leucogranites may correspond to liquids directly formed by partial melting of metasediments. Other types of granites involve other components or processes, such as restite unmixing from the source region, and/or interaction with mafic mantle-derived materials. Received: 11 July 1995 / Accepted: 27 February 1997     

Computer modeling of natural silicate melts: What can we learn from ab initio simulations

The structural and dynamical properties of four silicate liquids (silica, rhyolite, a model basalt and enstatite) are evaluated by ab initio molecular dynamics simulation using the density functional theory and are compared with classical simulations using a simple empirical force field. For a given composition, the structural parameters of the simulated melt vary little between the two calculations (ab initio versus empirical) and are in satisfactory agreement with structure data available in the literature. In contrast, ionic diffusivities and atomic vibration motions are found to be more sensitive to the details of the interactions. Furthermore, it is pointed out that the electronic polarization, as evaluated by the ab initio calculation, contributes significantly to the intensity of the infrared absorption spectra of molten silicates, a spectral feature which cannot be reproduced using nonpolarizable force field. However the vibration modes of TO₄ species and some structural details are not accurately reproduced by our ab initio calculation, shortcomings which need to be improved in the future.     

Defects and impurities in jarosite: A computer simulation study

Computer modelling techniques involving a rigid ion model have been used to investigate the defect structure and impurity site preferences in end-member K-jarosite. Calculated intrinsic vacancy energies show that the K₂SO₄ neutral cluster, with an energy per species of 1.34 eV, will be the most common defect in the pure phase. Defect reactions leading to vacancies on the Fe site have high energies, in excess of 4.0 eV per species, and are thus unlikely to occur in great numbers. However, the calculations show that divalent metal cations can be incorporated onto the Fe site via solution reactions with oxides leading to the formation of goethite. Calculated solution reactions are exothermic and thus predicted to be highly favourable. At K sites substitutions occur in the order Cd > Zn > Cu, but will be limited due to endothermic solution energies and structural considerations.     

Solution behavior of reduced COH volatiles in silicate melts at high pressure and temperature

The solubility and solution mechanisms of reduced COH volatiles in Na₂OSiO₂ melts in equilibrium with a (H₂ + CH₄) fluid at the hydrogen fugacity defined by the iron-wüstite + H₂O buffer [f_H2(IW)] have been determined as a function of pressure (1-2.5 GPa) and silicate melt polymerization (NBO/Si: nonbridging oxygen per silicon) at 1400 °C. The solubility, calculated as CH₄, increases from ∼0.2 wt% to ∼0.5 wt% in the melt NBO/Si-range ∼0.4 to ∼1.0. The solubility is not significantly pressure-dependent, probably because f_H2(IW) in the 1-2.5 GPa range does not vary greatly with pressure. Carbon isotope fractionation between methane-saturated melts and (H₂ + CH₄) fluid varied by ∼14‰ in the NBO/Si-range of these melts.The (C..H) and (O..H) speciation in the quenched melts was determined with Raman and ¹H MAS NMR spectroscopy. The dominant (C..H)-bearing complexes are molecular methane, CH₄, and a complex or functional group that includes entities with CCH bonding. Minor abundance of complexes that include SiOCH₃ bonding is tentatively identified in some melts. There is no spectroscopic evidence for SiC or SiCH₃. Raman spectra indicate silicate melt depolymerization (increasing NBO/Si). The [CH₄/CCH]^melt abundance ratio is positively correlated with NBO/Si, which is interpreted to suggest that the (CCH)-containing structural entity is bonded to the silicate melt network structure via its nonbridging oxygen. The ∼14‰ carbon isotope fractionation change between fluid and melt is because of the speciation changes of carbon in the melt.