Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs

Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523 K and 0.2 GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An₄₂Di₅₈ composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl₂ and MgCl₂ chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn₃O₄). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96 h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75 wt% Cl (saturation).However, products from short run duration experiments (<96 h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as “micronuggets”, increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 10³-10⁴ suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.     

Experimental study of the effect of SiO2 on Ni solubility in silicate melts

The solubility of Ni in silicate melts with variable SiO₂ content was studied at a total pressure of 1 atm within a wide range of temperature and oxygen fugacity. The maximum solubility of Ni (minimum activity coefficient of NiO) was observed in melts with ～55–57 wt % SiO₂, regardless of temperature and oxygen fugacity. Melts beyond this range showed significantly lower Ni solubility and, correspondingly, higher NiO activity coefficients. The analysis of our results and literature data led us to the conclusion that the NBO/T (number of nonbridging oxygen atoms per tetrahedrally coordinated atom) is inadequate to describe the effect of melt composition on Ni solubility.     

Effect of redox conditions on iron metal phase segregation during experimental high-temperature centrifuge modeling of the origin of the Moon’s core

The possible origin of the Moon’s metallic core at the precipitation of iron–sulfide phases during the partial melting of ultramafic material under various redox conditions was experimentally modeled by partially melting the model system olivine (85 wt %) + ferrobasalt (10 wt %) + metallic phase Fe₉₅S₅ (wt %) in a high-temperature centrifuge at 1430–1450°C. The oxygen fugacity fO₂ was determined from the composition of the quenched experimental silicate melts (glasses). A decrease in fO₂ is proved to be favorable for the segregation of iron–sulfide melt from the silicate matrix. The metallic phase is most effectively segregated in the form of melt droplets, and these droplets are accumulated in the lower portions of the samples under strongly reduced conditions, at fO₂ ～ 4.5–5.5 orders of magnitude lower than the iron–wüstite buffer.     

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.     

Nitrogen solubility in basaltic melt. Part I. Effect of oxygen fugacity

The role of the oxygen fugacity on the incorporation of nitrogen in basaltic magmas has been investigated using one atmosphere high temperature equilibration of tholeiitic-like compositions under controlled nitrogen and oxygen partial pressures in the [C-N-O] system. Nitrogen was extracted with a CO₂ laser under high vacuum and analyzed by static mass spectrometry. Over a redox range of 18 oxygen fugacity log units, this study shows that the incorporation of nitrogen in silicate melts follows two different behaviors. For log fO₂ values between −0.7 and −10.7 (the latter corresponding to IW − 1.3), nitrogen dissolves as a N₂ molecule into cavities of the silicate network (physical solubility). Nitrogen presents a constant solubility (Henry’s) coefficient of 2.21 ± 0.53 × 10⁻⁹ mol g⁻¹ atm⁻¹ at 1425°C, identical within uncertainties to the solubility of argon. Further decrease in the oxygen fugacity (log fO₂ between −10.7 and −18 corresponding to the range from IW − 1.3 to IW − 8.3) results in a drastic increase of the solubility of nitrogen by up to 5 orders of magnitude as nitrogen becomes chemically bounded with atoms of the silicate melt network (chemical solubility). The present results strongly suggest that under reducing conditions nitrogen dissolves in silicate melts as N³⁻ species rather than as CN⁻ cyanide radicals. The nitrogen content of a tholeiitic magma equilibrated with N₂ is computed from thermochemical processing of our data set as

     

Experimental constraints on Pt, Pd and Au partitioning and fractionation in silicate melt–sulfide–oxide–aqueous fluid systems at 800 °C, 150 MPa and variable sulfur fugacity

We have performed experiments to constrain the effect of sulfur fugacity (fS₂) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO₂) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS₂ = 0 to log fS₂ = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS₂ values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS₂. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS₂. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS₂. The data suggest that fS₂, working in concert with fO₂, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.     

Experimental study of the influence of SiO<Subscript>2</Subscript> on the solubility of cobalt and iron in silicate melts

The solubility of cobalt and iron in silicate melts with variable SiO₂ content was experimentally determined under controlled oxygen fugacity. It was shown that, independent of temperature and oxygen fugacity, the solubility of the two metals reaches a maximum (minimum of CoO and FeO activity coefficients) in melts of intermediate compositions. The analysis of available published data demonstrated that the γ_MeO values of at least four metals (Ni, Co, Fe, and Cr) dissolving in melts as divalent oxides show a minimum in melts with \(X_{SiO_2 } \) ≈ 57 ± 2 mol %. The position of the minimum is essentially independent of the element, melt temperature, and oxide concentration (from a few ppm to 13 wt%). The extremes of iron solubility (γ_FeO) in Fe-rich MgO-free melts may shift toward significantly lower \(X_{SiO_2 } \) values, although this inference requires additional experimental verification. Using a numerical example, some problems were discussed in the use of experimental data obtained in different laboratories for the development of a general model for the γ_MeO dependence on melt composition.     

Constraints on core formation from Pt partitioning in mafic silicate liquids at high temperatures

A new high temperature piston cylinder design has enabled the measurement of platinum solubility in mafic melts at temperatures up to 2500 °C, 2.2 GPa pressure, and under reducing conditions for 1-10 h. These high temperature and low f_O2 conditions may mimic a magma ocean during planetary core formation. Under these conditions, we measured tens to hundreds of ppm Pt in the quenched silicate glass corresponding to , 4-12 orders of magnitude lower than extrapolations from high f_O2 experiments at 1 bar and at temperatures no higher than 1550 °C. Moreover, the new experiments provide coupled textural and compositional evidence that noble metal micro-nuggets, ubiquitous in experimental studies of the highly siderophile elements, can be produced on quench: we measure equally high Pt concentrations in the rapidly quenched nugget-free peripheral margin of the silicate as we do in the more slowly quenched nugget-bearing interior region. We find that both temperature and melt composition exercise strong control on and that Pt⁰ and Pt¹⁺ may contribute significantly to the total dissolved Pt such that low f_O2 does not imply low Pt solubility. Equilibration of metal alloy with liquid silicate in a hot primitive magma might not have depleted platinum to the extent previously believed.     

Formation of N–С–О–Н molecules and complexes in the basalt–basaltic andesite melts at 1.5 Gpa and 1400°C in the presence of liquid iron alloys

The contents and speciation of nitrogen, carbon, and hydrogen were determined in basalt–basaltic andesite melts in equilibrium with liquid Fe alloys at 1.5 Gpa, 1400°C, and oxygen fugacity (fO₂) 1.4–1.9 log units below that of the Fe–FeO buffer (ΔlogfO₂(IW) =–1.4 …–1.9). Experiments were carried out on a piston- cylinder type apparatus using welded Pt capsules in the presence of excess С (graphite). Starting mixture consisted of natural ferrobasaltic glass and silicon nitride (Si₃N₄) as nitrogen source in the system. Experimental quench products representing glasses with spherical inclusions of iron alloy were analyzed using electron microprobe, Raman, and IR spectroscopy. With increase of Si₃N₄ in the starting mixture and, respectively, decrease of fO₂, silicate melt forming during experiments became depleted in FeO and enriched in SiO₂. It was established that the nitrogen content in the glasses increases from 0.13 to 0.44 wt % with decrease of ΔlogfO₂(IW) from–1.4 to–1.9, whereas C content in the first approximation remains constant within 1.18–1.13 wt %, while the total water content (ОН^– + Н₂О) determined by IR spectroscopy decreases from 4.91 to 1.20 wt %. The N (0.13–0.48 wt %) and C (0.75–2.26 wt %) contents determined in the Fe alloy show no clear correlation with fO₂. The IR and Raman spectroscopic study of the glasses indicates the formation of molecules and complexes with bonds N–H (NH₃, NH₂ ^?, NH₂ ⁺, NH₄ ⁺), Н–О (Н₂О, OH^–), С–Н (СН₄) as well as N₂ and Н₂ molecules in silicate melts. IR spectra also reveal the presence of complexes with С=О, С–N bonds and СО₂ molecules. Obtained data are compared with results of previous studies on the solubility and speciation of N, С, and Н in the model FeO–Na₂O–SiO₂–Al₂O₃ melts in equilibrium with liquid iron alloys at 1.5 GPa (1400°C) and 4 GPa (1550°C) (Kadik et al., 2011, 2015).     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

Solution behavior of C-O-H volatiles in FeO-Na2O-Al2O3-SiO2 melts in equilibrium with liquid iron alloy and graphite at 4 GPa and 1550°C

In order to elucidate the solution behavior of carbon and hydrogen in iron-bearing magmatic melts in equilibrium with a metallic iron phase and graphite at oxygen fugacity (fO₂) values 2–5 orders of magnitude below the iron-wustite buffer equilibrium, fO₂ (IW), experiments were carried out at 4 GPa and 1550°C with melts of FeO-Na₂O-SiO₂-Al₂O₃ compositions. Melt reduction in response to an fO₂ decrease was accompanied by a decrease in FeO content. The values of fO₂ in the experiments were determined on the basis of equilibrium between Fe-C-Si alloy and silicate liquid. Infrared and Raman spectroscopy showed that carbon compounds are formed in FeO-Na₂O-SiO₂-Al₂O₃ melts: CH₄ molecules, CH₃ complexes (Si-O-CH₃), and complexes with double C=O bonds. The content of CO₂ molecules and carbonate ions (CO ₃ ^2? ) is very low. In addition to carbon-bearing compounds, dissolved hydrogen occurs in melt as H₂ and H₂O molecules and OH^? groups. The spectral characteristics of FeO-Na₂O-SiO₂-Al₂O₃ glasses indicate the occurrence of redox reactions in the melt, which are accompanied at decreasing fO₂ by a significant decrease in H₂O and OH^?, a slight decrease in H₂, and a significant concomitant increase in CH₄ content. The content of species with the double C=O bond increases considerably at decreasing fO₂ and reaches a maximum at ΔlogfO₂(IW) = ?3. According to the obtained IR spectra, the total water content (OH^? + H₂O) in the glasses is 1.2–5.8 wt % and decreases with decreasing fO₂. The high H₂O contents are due largely to oxygen release related to FeO reduction in the melt. The total carbon content at high H₂O (4.9–5.8 wt %) is approximately 0.4 wt %. The carbon content in liquid iron alloys depends on silicon content and, probably, oxygen solubility and ranges from 0.3 to 3.65 wt %. Low carbon contents were observed at a significant increase in Si content in liquid iron alloy, which may be as high as ～13 wt % at fO₂ values 4–5 orders of magnitude below fO₂(IW).     

Solubility and solution mechanisms of C-O-H volatiles in silicate melt with variable redox conditions and melt composition at upper mantle temperatures and pressures

Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, f_H2, was controlled in the range between that of the iron-wüstite-H₂O (IW) and the magnetite-hematite-H₂O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH₃-groups forming bonds with Si⁴⁺ together with molecular CH₄. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Vanadium partitioning between orthopyroxene,spinel and silicate melt and the redox states of mantle source regions for primary magmas

The partitioning of V between orthopyroxene-liquid and spinel-liquid has been investigated in synthetic and natural mafic and ultramafic compositions as a function of temperature and oxygen fugacity (fO₂) at 100 kPa and in one experiment at higher pressure. The purpose of the experiments was to understand redox relationships for V in silicate melts with a view to deriving an empirical oxygen barometer for geochemically altered mafic and ultramafic magmas in the geologic record. Partitioning data for both orthopyroxene-liquid and spinel-liquid show profound changes at an fO₂ approximately 3 orders of magnitude below the nickel-nickel oxide (NNO) buffer, suggesting changes in the dominant valence state of V in silicate liquids from V³⁺ to V⁴⁺, near this fO₂.The results of the experiments on orthopyroxene-liquid are combined with published data for olivine-liquid and are applied to suites of mafic and ultramafic magmas that have equilibrated with a harzburgite residue in the mantle. The results show that Archean alumina-undepleted komatiites could have formed at fairly high oxygen fugacities, near ΔNNO ∼ 0, somewhat higher than Cretaceous komatiites and related picrites in the Caribbean region (between ΔNNO ∼ −1 to −3), and plume-related picrites from West Greenland (ΔNNO ∼ − 3). Picrites and boninites from convergent margins record the highest fO₂’s by this method, (ΔNNO = +1 to +2), consistent with other petrological estimates of their redox states. The approach developed in this study can thus provide estimates for the redox states of altered, mantle-derived magmas in the geological record, to which more conventional methods of oxygen barometry cannot be applied.     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.     

Platinum mineralization of the Svetly Bor and Nizhny Tagil intrusions,Ural Platinum Belt

This paper presents the results of a detailed mineralogical and micro analytical study of two Ural-Alaskan type intrusions in the Ural Platinum Belt: (1) the dunite-hosted mineralization of the Svetly Bor intrusion, and (2) the chromitite mineralization of the Nizhny Tagil intrusion. Two generations of platinum minerals are typical of both intrusions: magmatic Pt–Fe(Ni) alloys, and post-magmatic Pt(Fe,Ni,Cu) alloys. A trend from ferroan platinum to isoferroplatinum (Pt,Fe → Pt₃Fe) is shown for magmatic alloys of the Svetly Bor intrusion. Magmatic alloys of the Nizhny Tagil intrusion are represented by ferroan platinum (with Ni) only, varying in Fe. The magmatic Pt–Fe alloys of both intrusions were depleted in Fe during the evolution of ore-forming systems and crystallized during the entire magmatic process, generally as fine cubic crystals and anhedral grains hosted by dunite at the magmatic stage during and after the crystallization of dunite (platinum–dunite type of the Svetly Bor intrusion). The evolution of mineral paragenesis was accompanied by a temperature drop, as well as increases in fO₂ and fS₂.Most of the platinum was concentrated in the residual melts together with chromium, and crystallized in the final stage of the magmatic process (platinum–chromite ore of the Nizhny Tagil intrusion). Post-magmatic Pt(Fe,Cu,Ni) alloys formed during the serpentinization of dunite evolved according to a general compositional trend from tetraferroplatinum and ferronickelplatinum to tulameenite and later to Pt–Cu alloy and Pt-oxide (PtFe) → Pt(Fe,Cu,Ni) → Cu₃Pt → Pt–O. Platinum-rich mineralization of both intrusions was formed in the late magmatic stage from a melt rich in volatiles, regardless of their location in dunite or chromitites. Most probably, the rock structure (fracture systems) was the determining factor in the migration of PGE-rich residual melts and ore accumulation.     

Water solubility in haplogranitic melts coexisting with H2O-H2 fluids

The water solubility in haplogranitic melts (normative composition Ab₃₉Or₃₂Qz₂₉) coexisting with H₂O-H₂ fluids at 800 and 950 °C and 1, 2 and 3 kbar vapour pressure has been determined using IR spectroscopy. The experiments were performed in internally heated pressure vessels and the hydrogen fugacity (f _H2) was controlled using the double capsule technique and oxygen buffer assemblages (WM and IW). Due to the limited lifetimes of these oxygen buffers the water solubility was determined from diffusion profiles (concentration-distance profiles) measured with IR spectroscopy in the quenched glasses. The reliability of the experimental strategy was demonstrated by comparing the results of short- and long-duration experiments performed with pure H₂O fluids. The water solubility in Ab₃₉Or₃₂Qz₂₉ melts equilibrated with H₂O-H₂ fluids decreases progressively with decreasing f _H2O, as f _H2 (or X _H2) increases in the fluid phase. The effect of H₂ on the evolution of the water solubility is similar to that of CO₂ or another volatile with a low solubility in the melt and can be calculated in a first approximation with the Burnham water solubility model. Recalculation of high temperature water speciation for AOQ melts coexisting with H₂O-H₂ fluids at 800 °C, 2 kbar suggests that the concentrations of molecular H₂O are proportional to f _H2O (calculated using available mixing models), indicating Henrian behaviour for the solubility of molecular H₂O in haplogranitic melts. Received: 29 June 1998 / Accepted: 10 March 1999     

The effects of temperature,oxygen fugacity and melt composition on the behaviour of chromium in basic and ultrabasic melts

Chromite was equilibrated with two natural basic liquids and one natural ultrabasic liquid at temperatures and oxygen fugacities appropriate to geological conditions. The experiments were designed to document changes in mineral and glass compositions between the iron-wüstite and nickel-nickel oxide buffers, with special emphasis on conditions along quartz-fayalite-magnetite. The Cr contents of the melts at chromite saturation increase strongly with increasing temperature and with decreasing oxygen fugacity.A relationship is described which accounts for the compositional dependence of the partitioning of Cr between spinels and silicate melts by considering the exchange of FeCr₂O₄ component between the crystalline and melt phases. Interpretation of the data in terms of this exchange suggests that Cr³⁺ in metaluminous melts occurs in octahedrally coordinated sites, and that it does not depend on charge-balancing by monovalent cations. In this model, Cr³⁺ is proposed to behave like network-modifying Al³⁺ and Fe³⁺, i.e., the excess aluminum and ferric iron which do not participate in tetrahedrally coordinated matrix or network-forming complexes.The results can also be applied to the problem of the formation of massive chromitites of great lateral extent in basic layered intrusions. The data are consistent with a model in which the crystallization of chromite is initiated through magma mixing, in combination with the rapid heat loss associated with periodic influxes of magma into a chamber. An alternative model, in which chromite crystallization is initiated by repeated fluctuations in oxygen fugacity, is possible only if the magma f_O2 is not controlled by an oxygen buffer such as QFM.     

Platinum solubility and partitioning in a felsic melt-vapor-brine assemblage

The solubility and partitioning of Pt in a S-free vapor - brine - rhyolite melt - Pt metal assemblage has been quantified at 800 °C, f_O2=NNO and pressures of 100 and 140 MPa. Vapor and brine were sampled at run conditions by trapping these phases as glass-hosted fluid inclusions as the melt cooled through the glass transition temperature. The vapor and brine were in equilibrium with the melt at the time of trapping and, thus, represent fluids which were sampled at the termination of each experimental run. The microthermometrically determined salinities of vapor and brine are ∼2 and ∼63 wt.% NaCl eq. and ∼9 and ∼43 wt.% NaCl eq. at 100 and 140 MPa, respectively. Platinum solubilities in vapor, brine and glass (i.e., quenched melt) were quantified by using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS). Equilibrium is discussed with reference to the major and trace element concentrations of glass-hosted fluid inclusions as well as the silicate melt over run times that varied from 110 to 377 h at 140 MPa and 159 to 564 h at 100 MPa. Platinum solubility values (±1σ) in H₂O-saturated felsic melt are 0.28 ± 0.13 μg/g and 0.38 ± 0.06 μg/g at 140 and 100 MPa, respectively. Platinum solubility values () at 140 and 100 MPa, respectively, in aqueous vapor are 0.91 ± 0.29 μg/g and 0.37 ± 0.17 μg/g and in are brine 16 ± 10 μg/g and 3.3 ± 1.0 μg/g. The measured solubility data were used to calculate Nernst-type partition coefficients for Pt between vapor/melt, brine/melt and vapor/brine. The partition coefficient values () for vapor/melt, brine/melt and vapor/brine at 140 MPa are 2.9 ± 1.0, 67 ± 27, and 0.13 ± 0.05 and at 100 MPa are 1.0 ± 0.2, 6.8 ± 2.4, and 0.15 ± 0.05. The partitioning data were used to model the Pt-scavenging capacity of vapor and brine during the crystallization-driven degassing (i.e., second boiling) of a felsic silicate melt over a depth range (i.e., 3-6 km) consistent with the evolution of magmatic-hydrothermal ore deposits. Model calculations suggest that aqueous vapor and brine can scavenge sufficient quantities of Pt, and by analogy other platinum group elements (PGE), to produce economically important PGE-rich magmatic-hydrothermal ore deposits in Earth’s upper continental crust.