Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Liquid immiscibility in basic alkaline magmas

On the assumption that very basic silicate magmas contain appreciable amounts of O^2? ions, non-ideal mixing of the melt species may be due to strongly preferred ionic associations. The anions in the melt, O^2? on the one hand, and SiO₄^4? and polymerized aluminosilicate ionic species on the other, discriminate between the cations according to their field strength and polarizing power. K⁺, Na⁺, Ba²⁺, Sr²⁺ and Ca²⁺ associate with singly bonded oxygen, and Mg²⁺, Fe²⁺ and Ni²⁺ attach themselves to O^2? rather than to silicate or aluminosilicate anions. In extreme cases these relations may lead to unmixing in the silicate melt, especially in the presence of water which may lower the liquidus relative to the solvus temperature. Liquid—liquid phase separation in ultrabasic magmas may be related to the present model.     

High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

The enthalpies of solution of La₂O₃, TiO₂, HfO₂, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La₂O₃ in these silicate solvents is strongly exothermic and varies little with La₂O₃ concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO₂ is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti⁴⁺ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na⁺ by addition of Ni²⁺ or Cu²⁺. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.     

Structure and Composition Effects on the Oxygen Isotope Fractionation in Silicate Melts

The influence of melt composition and structure on the oxygen isotope fractionation was studied for the multicomponent (SiO₂ ± TiO₂ + Al₂O₃ ± Fe₂O₃ + MgO ± CaO) system at 1500°C and 1 atm. The experiments show that significant oxygen isotope effects can be observed in silicate melts even at such high temperature. It is shown that the ability of silicate melt to concentrate ¹⁸O isotope is mainly determined by its structure. In particular, an increase of the NBO/T ratio in the experimental glasses from 0.11 to 1.34 is accompanied by a systematic change of oxygen isotope difference between melt and internal standard by values from–0.85 to +1.29‰. The obtained data are described by the model based on mass-balance equations and the inferred existence of O⁰, O^–, and O^2– (bridging, non-bridging, and free oxygen) ions in the melts. An application of the model requires the intra-structure isotope fractionation between bridging and non-bridging oxygens. Calculations show that the intra-structure isotope fractionation in our experiments is equal to 4.2 ± 1.0‰. To describe the obtained oxygen isotope effects at the melts relatively to temperature and fraction of non-bridging oxygen a general equation was proposed.     

Effects of strong network modifiers on Fe<Superscript>3+</Superscript>/Fe<Superscript>2+</Superscript> in silicate melts: an experimental study

The effect of CaO, Na₂O, and K₂O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe³⁺/Fe²⁺ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO₂–TiO₂–Al₂O₃–FeO–Fe₂O₃–MgO–CaO–Na₂O–K₂O–P₂O₅ melts at air conditions.     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

Ferric/ferrous ratio in silicate melts: a new model for 1 atm data with special emphasis on the effects of melt composition

The effect of MgO and total FeO on ferric/ferrous ratio in model multicomponent silicate melts was investigated experimentally in the temperature range 1300–1500 °C at 1 atm total pressure in air. We demonstrate that the addition of these weak network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio in both mafic and silicic melts. Based on present and published experimental data, a new empirical equation is proposed to predict the ferric/ferrous ratio as a function of oxygen fugacity, temperature and melt composition. In contrast to previous equations, the compositional effect of melts on the Fe³⁺/Fe²⁺ ratio is not only modeled by the sum of the molar fraction of the individual oxide components. Additional interactions terms have also been incorporated. The main advantage of the proposed model is its applicability for a wide compositional range. However, its application to felsic melts (>?68 wt% SiO₂) is not recommended. Other advantages of this equation and differences when compared with previous models are discussed.     

Effect of network-forming cations on the oxygen isotope fractionation between silicate melts: Experimental study at 1400–1570°C

We have experimentally studied the behavior of oxygen isotope composition in silicate melts with a wide range of network-forming cations. Isotopic equilibration of the Di-An eutectic melts modified by addition of Si, Al, Ti, and Fe was carried out in a vertical tube furnace within a temperature range from 1400 to 1570°C. It was established that the value ^{10 3}Lnα between silicic and basic melts at 1400 and 1450°C systematically increases with increase of SiO₂ content, reaching ≈1‰ at 20% melt silica enrichment. The effect of the Fe₂O₃, TiO₂, and Al₂O₃ contents was studied at 1500°C. An increase in Fe₂O₃ from 5 to 20 wt % causes a 0.4‰ increase of δ¹⁸O. An increase in Ti and Al contents results in the non-linear behavior of δ¹⁸O, which decreases in the region of the highest TiO₂ (28.4%) and Al₂O₃ (29.3 %) contents. In the region of moderate Fe₂O₃, TiO₂, and Al₂O₃ contents, the values of δ¹⁸O show monotonous linear dependence on the oxide contents. Methods of estimations of oxygen isotope fractionation coefficients at T > 1400°C in the studied range of network-forming oxides are considered on the basis of experimental data. The calculation of fractionation coefficients with the use of I¹⁸O index showed that experimental values with increase of SiO₂ content deviate from calculated values by 0.3‰ for basic melts and 0.5–0.6‰ in the region of silicic melts. Similar pattern is observed during approximation of a melt by normative mineral composition. The calculation with the Garlick index leads to the systematic underestimation (on average, by 0.3‰) of 10³Lnα as compared to the experimental data. The NBO/T ratio appeared the best parameter to describe 10³Lnα in the melt-melt system, including the region of high-Fe melts. Analysis of experimental data leads us to conclude that the degree of polymerization of the melts in the studied temperature-composition region is the most important factor affecting the oxygen-isotope fractionation in the melt-melt system. Empirical index similar to the Garlick index was proposed to take into account oxygen associated with T-cations: $$I^m = (C_{Si} + aC_{Al} + bC_{Ti} + cC_{Fe^{3 + } } )/\Sigma C_i ,$$ where a, b, and c constants are empirically established coefficients: 0.75, 0. 70, and 1.75, respectively.     

Distribution of Mg2+ between olivine and silicate melt,and its implications regarding melt structure

Consideration of experimental data on the distribution of Mg²⁺ between olivine and silicate liquid clearly demonstrates that the distribution coefficient (K_Mg) is dependent upon variations in temperature, pressure and melt composition, largely because these variables control the solubility of Mg²⁺ in the melt phase. Attempts to minimize composition dependence of K_Mg, utilizing various activity-composition models for silicate melts, have been partially successful. Composition-related effects do not appear to be large, however, for melts of restricted range in composition (e.g., tholeiitic or lunar basalts) as long as the contents of alkalis and the alkali/alumina ratio are relatively small (on a molar basis). For such melts, K_Mg may be used as a reliable geothermometer. By analogy, these conclusions can be extended to the distribution of other divalent cation such as Fe²⁺, Mn²⁺, Ni²⁺ and Co²⁺.     

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.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Water and magmas; a mixing model

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

The structural role and homogeneous redox equilibria of iron in peraluminous,metaluminous and peralkaline silicate melts

The compositional dependence of the redox ratio (FeO/FeO_1.5) has been experimentally determined in K₂O-Al₂O₃-SiO₂-Fe₂O₃-FeO (KASFF) and K₂O-CaO-Al₂O₃-SiO₂-Fe₂O₃-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO₂. KASFF melts have from 1 to 5 mol % Fe₂O₃ and include both peraluminous (K₂O2O₃) and peralkaline (K₂O>Al₂O₃) compositions. KCASFF melts have 1 mol % Fe₂O₃ encompassing peraluminous, metaluminous (CaO+K₂O>Al₂O₃) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe₂O₃ have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K₂O/Al₂O₃). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K₂O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe³⁺ is in four-fold coordination, with K⁺ or Ca²⁺ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al³⁺ and Fe³⁺ for charge balancing cations in the latter melt. Tetrahedral Fe³⁺ is also less stable when Ca²⁺ provides local charge balance. The data are consistent with a network modifying role for Fe²⁺ in the melt.The data are interpreted to reflect the effects of melt composition on the partitioning of K⁺ and Ca²⁺ and Fe³⁺ and Al³⁺ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials Fe³⁺ Al_–1 and Ca_0.5K_–1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous melts as both (CaO+K₂O)/(CaO+K₂O+Al₂O₃) and K₂O/CaO decrease. These qualitative observations imply that minerals exhibiting these exchanges will also be similarly affected as liquid composition changes. Present address: Department of Geological Sciences, Virginia Tech, Blacksburg, VA 24061, USA     

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

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

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V³⁺ and V⁴⁺ in magnetite, and a mixture of IV- and VI-fold V⁵⁺ and V⁴⁺ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ?⁵¹V_mag-gl = ? 0.63?±?0.09‰ at FMQ ? 1 to ? 0.92?±?0.11‰ (SD) at ≈?FMQ?+?5, reflecting constant V³⁺/V⁴⁺ in magnetite but increasing V⁵⁺/V⁴⁺ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.     

Effect of pressure on the diffusivity of network-forming cations in melts of jadeitic compositions

The diffusivities of network-forming cations (Si⁴⁺, Al³⁺, Ge⁴⁺ and Ga³⁺) in melts of the jadeitic composition NaAl(Si, Ge)₂O₆ and Na(Al, Ga)Si₂O₆ have been measured at pressures between 6 and 20 kbar at 1400°C. The rates of interdiffusion of Si⁴⁺-Ge⁴⁺ and Al³⁺-Ge³⁺ increase with increasing pressure at constant temperature. The results are consistent with the ion-dynamics computer simulations of Jadeite melt by Angellet al. (1982, 1983). The coefficient measured for the Si⁴⁺-Ge⁴⁺ interdiffusion is between 8 × 10^?10 and 2.5 × 10^?8$\text{cm}{}^2\text{sec}$ at 6 kbar, depending on the composition of the melt, whereas at 20 kbar it is between 7 × 10^?9 and 2 × 10^?7$\text{cm}{}^2\text{sec}$. The effect of pressure is greater for more Si-rich compositions (i.e., closer to NaAlSi₂O₆ composition). The coefficient measured for the Al³⁺-Ga³⁺ inter- diffusion is between 9 × 10^?10 and 3 × 10^?9 cm²/sec at 6 kbar and between 3 × 10^?9 and 1 × 10^?8$\text{cm}{}^2\text{sec}$ at 20 kbar. The rate of increase in diffusivity with pressure of Al³⁺-Ga³⁺ (a factor of 3–4) is smaller than that of Si⁴⁺-Ge⁴⁺ (a factor of 7–17).The Si⁴⁺-Ge⁴⁺ interdiffusion in melts of Na₂O · 4(Si, Ge)O₂ composition has also been measured at 8 and 15 kbar for comparison. The effect of pressure on the diffusivity in this melt is significantly smaller than that for the jadeitic melts. The increase in diffusivity of the network-forming cations in jadeitic melts with increasing pressure may be related to the decrease in viscosity of the same melt. The present results, as well as the ion-dynamics simulations, suggest that the homogenization of partial melts and mixing of magmas would be more efficient at greater depths.     

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

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

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.