On the volume dependence of viscosity of some magmatic silicate melts

Summary Density and viscosity measurements of three melts of volcanic rock composition (basalt and andesite) at low temperatures were carried out to understand the role of free volume in the viscous behavior of a magma and to estimate the flow unit in the melts. The data combined with literature data suggest the following conclusion: free-volume theory is not applicable to these silicate melts; the relation between viscosity and the inverse of free volume does not yield a straight line in a wide temperature range from the glass-transion temperature to 1550°C. However, two depolymerized melts, diopside and Oki-Dozen alkali basalt (OAB), yield almost linear relationships. Thus, the free-volume theory should hold to a fairly good approximation for these two melts. Based on this approximation, the radius of flow unit for diopside melt was calculated to be about 4.7 Å, and that for Oki-Dozen alkali basalt to be about 4.2 Å. The three-dimensional silicate anions which may correspond to the flow unit are Si₁₄O₃₅ ^14– and Si₁₆O₄₀ ^16– for diopside melt, and Si₁₀O₂₅ ^10– and Si₁₂O₃₀ ^12– for OAB melt. The temperature effect on the initial slope of the viscosity-pressure relation has also been examined in the frame of free-volume theory. It was concluded that the relative increase of the initial slope of the relation with increasing temperature might be caused by the increase of free volume.With 6 Figures     

Transition metal ions in silicate melts—I. Manganese in sodium silicate melts

Optical absorption spectra obtained on glasses quenched from sodium silicate melts show Mn³⁺ to be the dominant species for melts heated in air and Mn²⁺ to be the dominant species for melts heated at Po₂ = 10^?17 bar. The absorption spectrum of Mn³⁺ consists of an intense band at 20,000cm^?1 with a 15,000cm^?1 satellite possibly arising from the Jahn-Teller effect. The independence of the spectrum from melt composition and the high band intensity is offered as evidence for a distinct Mn³⁺ complex in the melt. The spectrum of Mn²⁺ is weak and many expected bands are not observed. A two-band luminescence spectrum from Mn²⁺ has been tentatively interpreted as due to Mn²⁺ in interstitial sites in the network and Mn²⁺ coordinated by non-bridging oxygens.     

Modeling diffusive dissolution in silicate melts

Here empirical models for calculating self-diffusion coefficients and diffusion matrices are combined with MELTS, a thermodynamic model for silicate minerals and melts, to estimate diffusive dissolution rates, interface melt compositions and melt diffusivities. Simulations of olivine dissolution experiments in basalt show that the overall model is capable of accurately reproducing diffusive dissolution rates, and the resulting diffusion profiles, over a range of pressures and temperatures. However, the overall model is less successful at reproducing olivine dissolution in andesite, diopside dissolution in either basalt or andesite, or anorthite dissolution in picrite. Yet, even for these systems the predicted dissolution rates are generally within about a factor of two of the measured ones. Comparisons between simulations and experiments suggest that errors in the self-diffusion and thermodynamic models are responsible for the differences, and show that dissolution experiments could be a powerful way of testing and calibrating these and similar models. The overall model will also be a useful tool for designing future experiments, and for identifying the parameters that control diffusive dissolution (and crystallization) in silicate melts under a wide range of conditions.     

Activities of trace elements in silicate melts

A theoretical model has been developed which describes the amphoteric character of oxides in silicate melts. This has been used to account for the increased stability of the higher oxidation states of altervalent trace elements in silicate melts with increasing basicity and to derive a general expression for the estimation of trace element activities in silicate melts.     

The speciation of water in silicate melts

Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H₂O_molecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H₂O (vapor) = H₂O_molecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between f_H2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.     

Growth of diamond in hydrous silicate melts

This study demonstrates that a hydrous, halide bearing silicate melt is a viable medium for diamond growth. Experiments were conducted in the MgO–SiO₂–H₂O–C ± KCl ± NaCl system, which was used as a model for harzburgitic mantle. In no case did we observe crystals that could be interpreted as spontaneously nucleated, but growth of diamond on seed crystals at 1,400–1,600°C and 7 GPa in experiments of 4 h duration was observed. The addition of KCl to the system produced crystallization of diamond at temperatures as low as 1,400°C. At higher temperatures, larger growth features were produced than those that seen in the KCl-free system at the same conditions. The NaCl-bearing system is different; in these experiments, the diamond seed crystals show evidence of possible dissolution and layer growth, albeit more subdued growth than in the KCl system. Therefore, NaCl may be an inhibitor of diamond growth in a hydrous silicate melt. Based on these results, hydrous silicate melts could play a role in formation of diamond in either deep subduction zones, or above slabs imbricated against a lithospheric ‘root’ in the sub-continental lithospheric mantle. The water and halide necessary for their formation could be transported into the mantle in hydrous phases such as serpentine in subducting lithospheric slabs. Dehydration of serpentine at >200 km depth would release hydrous, halide-bearing fluids into the overlying mantle wedge or lithospheric root, triggering melting at conditions similar to those of the formation of natural diamond.     

Non-Newtonian rheology of homogeneous silicate melts

Several observations of non-Newtonian viscosity of silicate liquids at high stress or strain rates have been published in recent years. However, this phenomenon is not well understood yet. In this paper attention is drawn to the fact that steady state logarithmic values of reduced viscosities of silicate liquids under high stress show a linear dependence on the squared value of the applied stress. This relationship suggests that the elastic work done by the stress on the liquid is related to the observed viscosity decreases. It is shown that the development of non-Newtonian viscosity in silicate melts under high stress can be explained with the Adam and Gibbs (1965) theory, if one accepts that this elastic work generates configurational entropy.     

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.     

Viscosity and configurational entropy of silicate melts

With the configurational entropy theory of relaxation processes of Adam and Gibbs (1965), one predicts that the viscosity depends on temperature according to log $\text{η = A}{}_{\mathrm{e}}\text{+}\text{B}{}_{\mathrm{e}}\text{TS}{}_{\mathrm{<mtext>conf</mtext>}}$, where S_conf is the configurational entropy of the liquid. Thermochemical calculations of S_conf performed for some mineral compositions show the importance of non-configurational contributions to the entropy differences between amorphous and crystalline phases. Except for the case of SiO₂, the available thermodynamic data indicate that the above equation for viscosity accounts quantitatively for the experimentally determined temperature dependence of the viscosity of silicate melts. The Adam and Gibbs theory also provides a simple rationale for the non linear variation of the logarithmic viscosity with composition in mixed alkali silicate liquids at low temperatures, the minimum of viscosity resulting from the contribution of the entropy of mixing to S_conf.     

Rutile solubility and titanium coordination in silicate melts

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.     

Aluminum coordination in metaaluminous and peralkaline silicate melts

Incremental amounts of Na₂O and K₂O added to immiscible melts in the MgO-CaO-TiO₂-Al₂O₃ SiO₂ system cause a decrease in critical temperature, phase separation and change in the pattern of Al₂O₃ partitioning. Al₂O₃, which is concentrated in the low SiO₂ immiscible melts in the alkali-free system, is increasingly partitioned into the high-SiO₂ immiscible melt as the alkali/aluminium ratio is increased. However, K₂O is more effective than Na₂O in stabilizing Al₂O₂ in the SiO₂-rich melt. The coordination changes occurring in the aluminosilicate melts upon the addition of the alkali oxides are described by CaAl₂O₄+2SiOK=2KAlO₂+SiOCaOSi where K (or Na) displaces Ca as the charge-balancing cation for the networkforming AlO₄ tetrahedra. The increased stability of the AlO₄ species in the highly polymerized SiO₂-rich melt and the consequent shrinkage of the miscibility gap is ascribed to positive configurational entropy and negative enthalpy changes associated with the formation of K, Na-AlO₄ species. Element partition systematics indicate that (Na, K)AlO₂ species favor the more polymerized, CaAl₂O₄ and TiO₂ species, the less polymerized silicate structure in the melt.     

The mechanisms of water diffusion in polymerized silicate melts

Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz₂₉Or₇₁, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D _water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz₂₈Ab₃₈ Or₃₄, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, D_water is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H₂O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H₂O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H₂O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H₂O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of D_water versus water content implies that increases with water content. The change from linear to exponential dependence of D_water between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996     

Partitioning coefficients between olivine and silicate melts

Variation of Nernst partition coefficients (D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental ^{olivine/liquid}D data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO₂, H₂O, MgO and MgO/MgO + FeO^total. Values of ^{olivine/liquid}D generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO₂ content, but generally show poor correlations with other variables. Multi-element ^{olivine/liquid}D profiles calculated from regressions of D REE–Sc–Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D₀ (the strain compensated partition coefficient), E_M³⁺ (Young's Modulus), and r₀ (the size of the M site). Ln D₀ varies linearly with Ln MgO in the melt; E_M³⁺ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r₀ remains constant at 0.807 Å. These equations are then used to calculate ^{olivine/liquid}D for these elements using the Lattice Strain Model. These empirical parameterizations of ^{olivine/liquid}D variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The ^{olivine/liquid}D data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta–Hf–Zr–Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates.     

The onset of non-Newtonian rheology of silicate melts

The viscoelastic behavior of silicate melts has been measured for a range of compositions (NaAlSi₃O₈, NaCaAlSi₂O₇, CaMgSi₂O₆, Li₂Si₄O₉, Na₂Si₄O₉, K₂Si₄O₉, Na₂Si₃O₇, K₂Si₃O₇ and Na₂Si₂O₅) using the fiber elongation method. A1l compositions exhibit Newtonian behavior at low strain-rates, but non-Newtonian behavior at higher strain-rates, with strain-rate increasing faster than the applied stress. The decrease in shear viscosity observed at the high strain-rates ranges from 0.3 to 1.6 log₁₀ units (Pa s). The relaxation strain-rates, _relax, of these melts have been estimated from the low strain-rate, Newtonian, shear viscosity, using the Maxwell relationship; _relax= ^–1=(_s/G)^–1. For all compositions investigated, the onset of non-Newtonian rheology is observed at strain-rates 2.5+0.5 orders of magnitude less than the calculated relaxation strain-rate. This difference between the non-Newtonian onset and the relaxation strain-rate is larger than that predicted by the single relaxation time Maxwell model. Normalization of the experimental strain-rates to the relaxation strain-rate predicted from the Maxwell relation, eliminates the composition. and temperature-dependence of the onset of non-Newtonian behavior. The distribution of relaxation in the viscoelastic region appears to be unrelated to melt chemistry. This conclusion is consistent with the torsional, frequency domain study of Mills (1974) which illustrated a composition-invariance of the distribution of the imaginary component of the shear modulus in melts on the Na₂O-SiO₂ join. The present, time domain study of viscoelasticity contrasts with frequency domain studies in terms of the absolute strains employed. The present study employs relatively large total strains (up to 2). This compares with typical strains of 10^–8 in ultrasonic (frequency domain) studies. The stresses used to achieve the strain-rates required to observe viscoelastic behavior in this study approach the tensile strength of the fibers with the result that some of our experiments were terminated by fiber breakage. Although the breakage is unrelated to the observation of non-Newtonian viscosity, their close proximity in this and earlier studies suggests that brittle failure of igneous melts, may, in general, be preceded by a period of non-Newtonian rheology.     

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     

Immiscibility in magma and artificial silicate melts and glasses

Products of controlled smelting of basalt, andesite, granite, with and without additions of dolomite and/or catalysts, show tendencies toward liquation stratification, structural reorganization, microheterogeneities, microtextures, etc., under certain conditions, and in general, behavior which may resemble petrologically the natural liquation, crystallization, and mineralogenesis. -- V .P. Sokoloff.     

Experimental determination of the solubility of Au in silicate melts

Summary We report here new data on the solubility of Au in silicate melts of anorthite-diopside eutectic composition at a wide range of oxygen fugacities, from pure oxygen to 10^–8 atm, and at a temperature range of 1300 °C to 1480 °C. Because experiments were done with metal loops at temperatures above the Au-melting temperature, PdAu-metal-alloys had to be used. Pd-solubility data derived from the same set of experiments agree with earlier data obtained from experiments with pure Pd-metal (Borisov et al., 1994a). The results of the present experiments show that Pd-solubilities are by a factor of 2 to 6 higher than Au-solubilities. Both, Au and Pd solubilities decrease with decreasing oxygen fugacity. At oxygen fugacities below the iron-wiistite buffer (IW) Au solubility increases with decreasing fO₂ probably reflecting formation of Au-silicides at such reducing conditions. Compared to Pd, Au has higher activity coefficients in Fe-metal and lower solubility in silicate melts. This leads to similar metal-silicate partition coefficients for both elements. At a temperature of 1350 °C and an oxygen fugacity corresponding to IW-2 D^Au (met/sil) is about 2.5 · 10⁷ and D^Pd (met/sil) about 1.6 · 10⁷. Thus similar behavior is expected during metal separation in planetary bodies including core formation in the Earth. The metal/silicate partition coefficient of Ir is, however, by several orders of magnitudes higher (Borisov and Palme, 1995a). Equilibration with chondritic metal will therefore lead to grossly non-chondritic Pd/Ir or Au/Ir ratios in coexisting silicate phases. Chondritic ratios are thus indicative of the presence of unfractionated meteoritic components. Samples from the upper mantle of the Earth, for example, reflect the admixture of a late unfractionated (chondritic) veneer (e.g.,Kimura et al., 1974;Jagoutz et al., 1979).Solubilities of Pd and Au in silicate melts are much higher than the contents in terrestrial basalts implying that the abundances of these two elements are not buffered by residual PGE- and Au-containing alloys. The most likely process for fractionating PGEs in terrestrial magmas are mineral-melt (e.g., olivine/melt) equilibria.

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Experimentelle Bestimmung der Löslichkeit von Au in Silikatschmelzen

Zusammenfassung In der vorliegenden Arbeit wird über die Ergebnisse der Bestimmung der Löslichkeit von Au in Silikatschmelzen mit der Zusammensetzung des Anorthit-Diopsid Eutektikums berichtet. Die Versuche wurden mittels Metallschlaufe über einen weiten Sauerstoffpartialdruckbereich, von reinem Sauerstoff bis zu 10^–8 atm und in einem Temperaturbereich von 1300 °C bis 1480 °C, durchgeführt. Da diese Temperaturen jedoch den Au-Schmelzpunkt überschreiten, wurde mit AuPd-Legierungen gearbeitet. Die Ergebnisse der dadurch zusätzlich erhaltenen Pd-Versuche stimmen mit früher bestimmten, mit reinen Pd-Schlaufen durchgeführten Pd-Löslichkkeiten überein (Borisov et al., 1994a). Die auf reine Metalle zurückgerechneten Löslichkeiten von Pd sind um einen Faktor 2 bis 6 mal höher als die entsprechenden Au-Löslichkeiten. Die Löslichkeiten beider Metalle nehmen mit abnehmendem Sauerstoffpartialdruck ab. Unter noch stärker reduzierenden Bedingungen (Eisen-Wüstit Gleichgewicht) nimmt die Löslichkeit von Au jedoch zu. Dies könnte auf die Bildung von Au-Siliziden zurückzuführen sein.Im Vergleich zu Pd sind die Aktivitätskoeffizienten von Au in metallischem Eisen höher, die Löslichkeiten in Silikatschmelzen jedoch niedriger. Das führt zu ähnlichen Metall/Silikat Verteilungskoeffizienten von Au und Pd. Bei einer Temperatur von 1350 °C und einer Sauerstoffugazität von IW-2 ergeben sich für D^Au (met/sil) 2.5 · 10⁷ und für D^Pd (met/sil) 1.6* 10⁷. Der Metall/Silikat-Verteilungskoeffizient von Ir ist jedoch unter den gleichen Bedingungen um mehrere Größenordnungen höher (Borisov andPalme, 1995a). Ein chondritisches Pd/Ir- oder Au/Ir-Verhältnis kann also auf die Anwesenheit einer unfraktionierten chondritischen Komponente zurückgeführt werden. Dies gilt beispielsweise für Proben aus dem oberen Erdmantel. Hier handelt es sich vermutlich um Zumischung einer späten chondritischen Akkretionskomponente, die sich nicht mehr mit einer metallischen Phase (Kern) ins Gleichgewicht gesetzt hat (z.B.Kimura et al., 1974,Jagoutz et al., 1979).Die Löslichkeiten von Pd und Au in Silikatschmelzen sind wesentlich höher als ihre Gehalte in basaltischen und komatiitischen Laven. Dies bedeutet, daß Au und Pd in Schmelzen aus dem Erdmantel nicht durch residuale Au- und/oder Pd-haltige Metall phasen bestimmt sind. Gleichgewichte zwischen Schmelze und Mineralen (z.B. Olivin) sind die wahrscheinlichsten Fraktionierungsmechanismen für Platingruppenelemente in terrestrischen Magmen.

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With 5 Figures