Experimental study of platinum solubility in silicate melt to 14 GPa and 2273 K: Implications for accretion and core formation in Earth

We determined the solubility limit of Pt in molten haplo-basalt (1 atm anorthite-diopside eutectic composition) in piston-cylinder and multi-anvil experiments at pressures between 0.5 and 14 GPa and temperatures from 1698 to 2223 K. Experiments were internally buffered at ∼IW + 1. Pt concentrations in quenched-glass samples were measured by laser-ablation inductively coupled-plasma mass spectrometry (LA-ICPMS). This technique allows detection of small-scale heterogeneities in the run products while supplying three-dimensional information about the distribution of Pt in the glass samples. Analytical variations in ¹⁹⁵Pt indicate that all experiments contain Pt nanonuggets after quenching. Averages of multiple, time-integrated spot analyses (corresponding to bulk analyses) typically have large standard deviations, and calculated Pt solubilities in silicate melt exhibit no statistically significant covariance with temperature or pressure. In contrast, averages of minimum ¹⁹⁵Pt signal levels show less inter-spot variation, and solubility shows significant covariance with pressure and temperature. We interpret these results to mean that nanonuggets are not quench particles, that is, they were not dissolved in the silicate melt, but were part of the equilibrium metal assemblage at run conditions. We assume that the average of minimum measured Pt abundances in multiple probe spots is representative of the actual solubility. The metal/silicate partition coefficients (D^met/sil) is the inverse of solubility, and we parameterize D^met/sil in the data set by multivariate regression. The statistically robust regression shows that increasing both pressure and temperature causes D^met/silto decrease, that is, Pt becomes more soluble in silicate melt. D^met/sil decreases by less than an order of magnitude at constant temperature from 1 to 14 GPa, whereas isobaric increase in temperature produces a more dramatic effect, with D^met/sil decreasing by more than one order of magnitude between 1623 and 2223 K. The Pt abundance in the Earth’s mantle requires that D^met/sil is ∼1000 assuming core-mantle equilibration. Geochemical models for core formation in Earth based on moderately and slightly siderophile elements are generally consistent with equilibrium metal segregation at conditions generally in the range of 20-60 GPa and 2000-4000 K. Model extrapolations to these conditions show that the Pt abundance of the mantle can only be matched if oxygen fugacity is high (∼IW) and if Pt mixes ideally in molten iron, both very unlikely conditions. For more realistic values of oxygen fugacity (∼IW − 2) and experimentally-based constraints on non-ideal mixing, models show that D^met/sil would be several orders of magnitude too high even at the most favorable conditions of pressure and temperature. These results suggest that the mantle Pt budget, and by implication other highly siderophile elements, was added by late addition of a ‘late veneer’ phase to the accreting proto-Earth.     

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.     

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.     

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.     

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.     

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.     

Platinum solubility in a haplobasaltic melt at 1250°C and 0.2 GPa: The effect of water content and oxygen fugacity

Haplobasaltic melts with a 101 kPa dry eutectic composition (An₄₂Di₅₈) and varying water contents were equilibrated with their platinum capsule at 1523 K and 200 MPa in an internally heated pressure vessel (IHPV) equipped with a rapid quench device. Experimental products were inclusion-free glasses representative of the Pt-saturated silicate melts at the experimental conditions. Platinum concentrations were determined using an isotope dilution multicollector inductively coupled plasma mass spectrometer and water contents and distribution by Karl Fischer titration and Fourier transform infrared spectroscopy, respectively.The water content of the melt has no intrinsic effect on platinum solubility, for concentrations between 0.9 wt.% and 4.4 wt.% H₂O (saturation). Platinum solubility increases with increasing water content, but this effect is an indirect effect because increasing water content at fixed f_H2 (imposed by the IHPV) increases the oxygen fugacity of the experiment.The positive oxygen fugacity dependence of Pt solubility in a hydrous silicate melt at 200 MPa is identical to that in anhydrous melts of the same composition determined in previous studies at 101 kPa. This study extends the range of platinum solubilities to oxygen fugacities lower than was previously possible. Combining the data of this and previous studies, Pt solubility is related to oxygen fugacity (in bar) at 1523 K by the equation:

[Pt]_total(ppb)=1389×f_O2+7531×(f_O2)^1/2     

Solubility of palladium in picritic melts: 1. The effect of iron

In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO₂ at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO₂ of FMQ the slope in log Pd concentration vs. log pO₂ space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO₂ range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO₂ (FMQ+0.5) Pd concentrations significantly increase with increasing X_FeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd²⁺ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents.     

Dynamic crystallization of shock melts in Allan Hills 77005: Implications for melt pocket formation in Martian meteorites

A series of crystallization experiments have been performed on synthetic glasses matching the composition of a melt pocket found in Allan Hills (ALH) 77005 in order to evaluate the heterogeneous nucleation potential of the melt and the effect of oxygen fugacity on crystallization. The starting temperature of the experiments varied from superliquidus, liquidus and subliquidus temperatures. Each run was then cooled at rates of 10, 500 and 1000 °C/h at FMQ. The results of this study constrain the heating and cooling regime for a microporphyritic melt pocket. Within the melt pocket, strong thermal gradients existed at the onset of crystallization, giving rise to a heterogeneous distribution of nucleation sites resulting in gradational textures of olivine and chromite. Skeletal olivine in the melt pocket center crystallized from a melt containing few nuclei cooled at a fast rate. Nearer to the melt pocket margin elongate skeletal shapes progress to hopper and equant euhedral, reflecting an increase in nuclei in the melt at the initiation of crystallization and growth at low degrees of supercooling. Cooling from post-shock temperatures took place on the order of minutes.An additional series of experiments were conducted for a melt temperature of 1510 °C and a cooling rate of 500 °C/h at the FMQ buffer, as well as 1 and 2 log units above and below FMQ. Variation in chromite stability in these experiments is reflected in crystal shapes and composition, and place constraints on the oxygen fugacity of crystallization of the melt pocket. We conclude that the oxygen fugacity of the melt pocket was set by the Fe³⁺/Fe²⁺ ratio imparted by melting of the host rock, rather than external factors such as incorporation of CO₂-rich Martian atmosphere, or melting and injection of oxidized surface (e.g., regolith) material.Comparison with previous crystallization experiments on melt pockets in Martian basalts indicate that the predominance of dendritic crystal shapes reflects the likelihood that those melt pockets with lower liquidus temperatures will be more completely melted, destroying most or all nuclei in the melt. In this case, crystal growth takes place at high degrees of supercooling, yielding dendritic shapes. It appears as though the melting process is just as important as cooling rate in determining the final texture of the melt pocket, as this process controls elimination or preservation of nuclei at the onset of cooling and crystallization.     

Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, 8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite.A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe₈₅Ni₁₄Co₁) trapped within the glass beads indicates a log oxygen fugacity of −11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this f_O2 corresponds to a minimum pressure of 41 MPa on the graphite–C–O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe–FeO activity model for the natural A17 orange glass–metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many lunar basalts and the ubiquitous Fe-metal in these rocks are also likely generated by the oxidation of carbon. The presence of carbon in the lunar basalts and the recent discovery of ppm levels of water in lunar basalts indicate that at least parts of the lunar interior still contained volatiles at 3.9 bybp.     

The distribution of sulfur between haplogranitic melts and aqueous fluids

The distribution of sulfur between haplogranitic melt and aqueous fluid has been measured as a function of oxygen fugacity (Co-CoO-buffer to hematite-magnetite buffer), pressure (0.5-3 kbar), and temperature (750-850 °C). Sulfur always strongly partitions into the fluid. At a given oxygen fugacity, pressure and temperature, the distribution of sulfur between melt and fluid can be described by one constant partition coefficient over a wide range of sulfur concentrations. Oxygen fugacity is the most important parameter controlling sulfur partitioning. While the fluid/melt partition coefficient of sulfur is 468 ± 32 under Co-CoO buffer conditions at 2 kbar and 850 °C, it decreases to 47 ± 4 at an oxygen fugacity 0.5-1 log unit above Ni-NiO at the same pressure and temperature. A further increase in oxygen fugacity to the hematite-magnetite buffer has virtually no effect on the partition coefficient (D^fluid/melt = 49 ± 2). The dependence of D^fluid/melt on temperature and pressure was systematically explored at an oxygen fugacity 0.5-1 log units above Ni-NiO. At 850 °C, the effect of pressure on the partition coefficient is small (D^fluid/melt = 58 ± 3 at 0.5 kbar; 94 ± 9 at 1 kbar; 47 ± 4 at 2 kbar and 68 ± 5 at 3 kbar) and temperature also has only a minor effect on partitioning.The data show the “sulfur excess” observed in many explosive volcanic eruptions can easily be explained by the presence of a small fraction of hydrous fluid in the magma chamber before the eruption. The sulfur excess can be calculated as the product of the fluid/melt partition coefficient of sulfur and the mass ratio of fluid over melt in the erupted material. For a plausible fluid/melt partition coefficient of 47 under oxidizing conditions, a 10-fold sulfur excess corresponds to a 17.6 wt.% of fluid in the erupted material. Large sulfur excesses (10-fold or higher) are only to be expected if only a small fraction of the magma residing in the magma chamber is erupted.The behavior of sulfur, which seems to be largely independent of pressure and temperature under oxidizing conditions is very different from chlorine, where the fluid/melt partition coefficient strongly increases with pressure. Variations in the SO₂/HCl ratio of volcanic gases, if they reflect primary processes in the magma chamber, therefore provide an indicator of pressure variations in a magma. In particular, major increases in the S/Cl ratio of an aqueous fluid coexisting with a felsic magma suggest a pressure reduction in the magma chamber and/or magma rising to the surface.     

The combined effects of chlorine and fluorine on the viscosity of aluminosilicate melts

The effect of fluorine and fluorine + chlorine on melt viscosities in the system Na₂O-Fe₂O₃-Al₂O₃-SiO₂ has been investigated. Shear viscosities of melts ranging in composition from peraluminous [(Na₂O + FeO) < (Al₂O₃ + Fe₂O₃)] to peralkaline [(Na₂O + FeO) > (Al₂O₃ + Fe₂O₃)] were determined over a temperature range 560-890 °C at room pressure in a nitrogen atmosphere. Viscosities were determined using the micropenetration technique in the range of 10^8.8 to 10^12.0 Pa s. The compositions are based on addition of FeF₃ and FeCl₃ to aluminosilicate melts with a fixed amount of SiO₂ (67 mol%). Although there was a significant loss of F and Cl during glass syntheses, none occurred during the viscometry experiments. The presence of fluorine causes a decrease in the viscosity of all melts investigated. This is in agreement with the structural model that two fluorines replace one oxygen; resulting in a depolymerisation of the melt and thus a decrease in viscosity. The presence of both chlorine and fluorine results in a slight increase in the viscosity of peraluminous melts and a decrease in viscosity of peralkaline melts. The variation in viscosity produced by the addition of both fluorine and chlorine is the opposite to that observed in the same composition melts, with the addition of chlorine alone (Zimova M. and Webb S.L. (2006) The effect of chlorine on the viscosity of Na₂O-Fe₂O₃-Al₂O₃-SiO₂ melts. Am. Mineral.91, 344-352). This suggests that the structural interaction of chlorine and fluorine is not linear and the rheology of magmas containing both volatiles is more complex than previously assumed.     

Solubility of CO2 in a Ca-rich leucitite: effects of pressure,temperature, and oxygen fugacity

The solubility of carbon dioxide in a Ca-rich leucitite has been investigated as a function of pressure (0.1–2.0 GPa), temperature (1200–1600°C), and oxygen fugacity. The experiments were done in a rapid-quench internally-heated pressure vessel (0.1 GPa) and a piston cylinder (0.5–2.0 GPa). The leucitite glass, previously equilibrated at NNO, and silver oxalate were loaded in Fe-doped Pt capsules (oxidized conditions) and graphitelined Pt capsules (reduced conditions). Secondary Ion Mass Spectrometry and bulk carbon analyses were used to determine the amount of dissolved carbon. Speciation of carbon was characterized by Fourier transform microinfrared spectroscopy. At oxidized conditions, only CO₃ ^2- is observed as a dissolved species. The solubility is high with CO₂ contents in the melt attaining 6.2 wt% at 2.0 GPa and 1350°C. The solubility increases with pressure and shows a significant negative temperature dependence. An excellent correlation is obtained when the data are fit to a model, based on the simplified solubility reaction CO₂ ^(vapor)+O^2-(melt)CO₃ ^2-(melt), which describes the solubility of CO₂ as a function of pressure, temperature and fCO₂. At reduced conditions, the amount of carbon dissolved is significantly lower, and CO₃ ^2- is still the only species present in the melt. If the solubility model established at oxidized conditions is applied, the carbon dissolved appears to be essentially a function of fCO₂ alone although divergence increases in a consistent manner with pressure and temperature. This could suggest a low but significant solubility of CO with a positive temperature dependence or a departure of the calculated fluid compositions determined by the equation of state from the actual ones. The strong preferential solubility of carbon in its oxidized C⁴⁺ form, even at reduced conditions, implies that ascending melts with high CO₂ solubility can experience significant oxidation through degassing. This could reconcile the oxidized nature of some Ca-rich alkaline magmas with more reduced mantle source regions.     

Controls on gold solubility in arc magmas: An experimental study at 1000 °C and 4 kbar

In order to (1) explain the worldwide association between epithermal gold-copper-molybdenum deposits and arc magmas and (2) test the hypothesis that adakitic magmas would be Au-specialized, we have determined the solubility of Au at 4 kbar and 1000 °C for three intermediate magmas (two adakites and one calc-alkaline composition) from the Philippines. The experiments were performed over a fO₂ range corresponding to reducing (∼NNO−1), moderately oxidizing (∼NNO+1.5) and strongly oxidizing (∼NNO+3) conditions as measured by solid Ni-Pd-O sensors. They were carried out in gold containers, the latter serving also as the source of gold, in presence of variable amounts of H₂O and, in a few additional experiments, of S. Concentrations of Au in glasses were determined by LA-ICPMS. Gold solubility in melt is very low (30-240 ppb) but increases with fO₂ in a way consistent with the dissolution of gold as both Au¹⁺ and Au³⁺ species. In the S-bearing experiments performed at ∼NNO−1, gold solubility reaches much higher values, from ∼1200 to 4300 ppb, and seems to correlate with melt S content. No systematic difference in gold solubility is observed between the adakitic and the non-adakitic compositions investigated. Oxygen fugacity and the sulfur concentration in melt are the main parameters controlling the incorporation and concentration of gold in magmas. Certain adakitic and non-adakitic magmas have high fO₂ and magmatic S concentrations favorable to the incorporation and transport of gold. Therefore, the cause of a particular association between some arc magmas and Au-Cu-Mo deposits needs to be searched in the origin of those specialized magmas by involvement of Au- and S-rich protoliths. The subducted slab, which contains metal-rich massive sulfides, may constitute a potentially favorable protolith for the genesis of magmas specialized with respect to gold.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Temperature dependence of Pt and Rh solubilities in a haplobasaltic melt

The temperature dependence of the solubilities of Pt and Rh in a haplobasaltic (anorthite-diopside 1-bar eutectic composition) melt has been investigated at 1 bar and 1300 to 1550°C using the mechanically assisted equilibration technique (Dingwell et al., 1994). The experiments were performed at almost constant oxygen fugacity (log fO₂ = −2.5 ± 0.3) over the entire temperature range. Major element concentrations in the quenched glass samples were determined using an electron microprobe. Pt and Rh concentrations were obtained by laser ablation inductive coupled plasma mass spectrometry. From our data, we obtain the following expressions for the solubilities of pure Pt and pure Rh in anorthite-diopside eutectic melt at 1 bar and log fO₂ = −2.5:

     

Na2O solubility in CaO-MgO-SiO2 melts

The sodium solubility in silicate melts in the CaO-MgO-SiO₂ (CMS) system at 1400 °C has been measured by using a closed thermochemical reactor designed to control alkali metal activity. In this reactor, Na_(g) evaporation from a Na₂O-xSiO₂ melt imposes an alkali metal vapor pressure in equilibrium with the molten silicate samples. Because of equilibrium conditions in the reactor, the activity of sodium-metal oxide in the molten samples is the same as that of the source, i.e., aNa₂O_(sample) = aNa₂O_(source). This design also allows to determine the sodium oxide activity coefficient in the samples. Thirty-three different CMS compositions were studied. The results show that the amount of sodium entering from the gas phase (i.e., Na₂O solubility) is strongly sensitive to silica content of the melt and, to a lesser extent, the relative amounts of CaO and MgO. Despite the large range of tested melt compositions (0 < CaO and MgO < 40; 40 < SiO₂ < 100; in wt%), we found that Na₂O solubility is conveniently modeled as a linear function of the optical basicity (Λ) calculated on a Na-free basis melt composition. In our experiments, γNa₂O_(sample) ranges from 7 × 10⁻⁷ to 5 × 10⁻⁶, indicating a strongly non-ideal behavior of Na₂O solubility in the studied CMS melts (γNa₂O_(sample) ? 1). In addition to showing the effect of sodium on phase relationships in the CMS system, this Na₂O solubility study brings valuable new constraints on how melt structure controls the solubility of Na in the CMS silicate melts. Our results suggest that Na₂O addition causes depolymerization of the melt by preferential breaking of Si-O-Si bonds of the most polymerized tetrahedral sites, mainly Q⁴.     

The solubility of gold in hydrogen sulfide gas: An experimental study

The solubility of gold in H₂S gas has been investigated at temperatures of 300, 350 and 400 °C and pressures up to 230 bars. Experimentally determined values of the solubility of Au are 0.4-1.4 ppb at 300 °C, 1-8 ppb at 350 °C and 8.6-95 ppb at 400 °C. Owing to a positive dependence of the logarithm of the fugacity of gold on the logarithm of the fugacity of H₂S, it is proposed that the solubility of Au can be attributed to formation of a solvated gaseous sulfide or bisulfide complex through reactions of the type:

(A)     

The solubility of copper in high-temperature magmatic vapors: A quest for the significance of various chloride and sulfide complexes

We conducted experiments to determine the effect of various chemical components (NaCl, KCl, HCl, FeCl₂, H₂S, SO₂) on the solubility of Cu in single phase aqueous vapors at 1000 °C and 150 MPa. The experiments were conducted in Au₉₇Cu₃ alloy capsules buffering Cu activities at 0.01. The volatile phase was sampled at run conditions by the entrapment of synthetic fluid inclusions in quartz. To test if the volatile phase had reached equilibrium before the isolation of the inclusions by fracture healing, we trapped two inclusion generations, one in an initially prefractured chip and another in a quartz chip that was fractured in situ during the experiments. The synthetic fluid inclusions were subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry. In pure water, the apparent solubility of Cu is below the limits of detection of 6 μg/g, showing the low stability of hydroxy Cu complexes at our experimental conditions. The presence of alkali chlorides supports modest Cu solubility likely in the form of NaCuCl₂ and KCuCl₂ complexes. In the H₂O-H₂S (+SiO₂ and Au₉₇Cu₃) system at an fH₂S of 10.4 MPa the apparent solubility of Cu is lower by a factor of ∼5 than that in a S-free 0.5 m NaCl solution, showing that copper hydrosulfide complexes are only moderately stable at these conditions. Addition of 4.7 mol% of sulfur to the H₂O-NaCl system at an fO₂ of 0.4 log units below the Ni-NiO buffer, yielding dominantly H₂S species, results in only a moderate increase in apparent Cu solubility, which diminishes in the presence of HCl. The addition of KCl results in a strong increase of apparent Cu solubility in the presence of H₂S. The solubility of Cu increases with the fugacity of oxygen in both the H₂O-NaCl and the H₂O-S-NaCl system following an approximately fourth root relationship as expected based on the stoichiometry of the involved redox reactions. Replacement of NaCl by FeCl₂ exerted only a minor effect on the Cu solubility.Results of our experiments, combined with thermochemical data obtained by ab initio quantum chemical calculations, suggest dissolution of Cu dominantly as Na(/K)CuCl₂, Na(/K)Cu(HS)_2, H₂SCuHS, and Na(/K)ClCuHS, the relative abundance of which are dictated by the H₂S/total chloride and HCl/alkali chloride ratios.     

The experimental calibration of the iron isotope fractionation factor between pyrrhotite and peralkaline rhyolitic melt

A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using ⁵⁷Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H₂O) and natural pyrrhotites (Fe_1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ ⁵⁶Fe/⁵⁴Fe_{pyrrhotite-melt} = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe²⁺/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe²⁺/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.