Solubilities of nitrogen and noble gases in silicate melts under various oxygen fugacities: implications for the origin and degassing history of nitrogen and noble gases in the earth

Solubility experiments for nitrogen and noble gases (Ar and Ne) in silicate melts were conducted using two experimental configurations: one was conducted at 1 atmospheric pressure, T =1300°C and oxygen fugacity (fO₂) of IW + 0.9 (i.e., 0.9 log units higher than the iron-wüstite buffer) and the other at high pressures (P_total ∼ 2 × 10⁸ Pa), 1500°C and fO₂ ∼ IW + 6. For the former experiment, isotopically labeled-nitrogen (¹⁵N¹⁵N-enriched) was used to distinguish dissolved nitrogen from contaminating atmospheric or organic nitrogen and to examine dissolution mechanisms of nitrogen in silicate melts. The results obtained for the two series of experiments are consistent with each other, suggesting that Henry's law is satisfied for fN₂ of up to ∼250 atm (2.5 × 10⁷ Pa). The results are also consistent with our earlier results (Miyazaki et al., 1995) obtained at highly oxidizing conditions (fO₂ ∼ IW + 10). All these results support physical dissolution of nitrogen as N₂ molecules in silicate melts for fO₂ from ∼IW + 10 down to ∼IW. The observed solubility (Henry's constant) of nitrogen (3-5 × 10⁻⁹ mol/g/atm) is comparable to that of Ar (2-4 × 10⁻⁹ mol/g/atm), and much lower than that of Ne (11-14 × 10⁻⁹ mol/g/atm) at 1300°C. A preliminary experiment was also performed for partitioning of nitrogen and noble gases between clinopyroxene (cpx) and basaltic melt using a piston cylinder-type apparatus at 1.5 GPa and at 1270 to 1350°C. The obtained cpx/melt partition coefficient of nitrogen is 0.06, slightly lower than those of noble gases (∼0.1 for Ne to Xe), suggesting that nitrogen is as incompatible as or even slightly more incompatible than noble gases. The present results imply that a large nitrogen/Ar fractionation would not be produced by magmatic processes. Therefore, the two orders of magnitude difference between the N₂/³⁶Ar ratios in the Earth's atmosphere (∼10⁴) and that in the mantle (∼10⁶) must be explained by some other processes, such as incomplete segregation of metal blobs into the core and their later oxidation.     

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 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.     

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).     

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     

Oxygen fugacity dependence of Os solubility in haplobasaltic melt

Os equilibrium solubilities were determined at 1350 °C over a wide range of oxygen fugacities (−12 < log fO₂ < −7) applying the mechanically assisted equilibration technique (MAE) at 10⁵ Pa (= 1 bar). Os concentrations in the glass samples were analysed using ID-NTIMS. Additional LA-ICP-MS and SEM analyses were performed to detect, visualize and analyse the nature and chemistry of “nanonuggets.” Os solubilities determined range at a constant temperature of 1350 °C from 0.63 ± 0.04 to 37.4 ± 1.16 ppb depending on oxygen fugacity. At the highest oxygen fugacities, Os³⁺ can be confirmed as the main oxidation state of Os. At low oxygen fugacities (below log fO₂ = −8), samples are contaminated by nanonuggets which, despite the MAE technique, were still not removed entirely from the melt. However, the present results indicate that applying MAE technology does reduce the amount of nanonuggets present significantly, resulting in the lowest Os solubility results reported to date under these experimental conditions, and extending the experimentally accessible range of fO₂ for these studies to lower values. Calculated metal/silicate melt partition coefficients are therefore higher compared to previous studies, making Os more siderophile. Neglecting the as yet unknown temperature dependence of the Os metal/silicate melt partition coefficient, extrapolation of the obtained Os solubilities to conditions for core-mantle equilibrium, results in a , while metallic alloy/silicate melt partition coefficients range from 1.4 × 10⁶ to 8.6 × 10⁷, in agreement with earlier findings. Therefore remains too high by 2-4 orders of magnitude to explain the Os abundance in the Earth’s mantle as result of core-mantle equilibrium during core formation.     

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.     

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:

     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Liquidus karrooite stability and composition at reducing conditions

We have determined the stability of rutile and karrooite on the liquidus of pseudobinary silicate melts of anorthite–diopside eutectic composition with, in addition, of up to 32 wt% TiO₂ at one atm total pressure and at wide range of oxygen fugacities. At 1,300°C and at an fO₂ below 10^–11.2 atm rutile (TiO₂) is replaced as liquidus phase by the pseudobrookite-type MgTi₂O₅–Ti₃O₅ solid solution with some Al in the crystal structure. The composition of karrooite was found to be strongly dependent on oxygen fugacity. Crystalline phases were identified by transmission electron microscopy (TEM). The results obtained in this study are relevant for understanding the chemistry of lunar armalcolites. Using excess rutile solubility at reducing conditions, we estimated the Ti⁴⁺ /Ti³⁺ ratio in silicate melts at 1,300°C as function of fO₂.     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.     

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.     

The solution behavior of H2O in peralkaline aluminosilicate melts at high pressure with implications for properties of hydrous melts

Solubility and solution mechanisms of H₂O in depolymerized melts in the system Na₂O-Al₂O₃-SiO₂ were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na₂Si₄O₉-Na₂(NaAl)₄O₉] with Al/(Al+Si) = 0.00-0.25. The H₂O solubility was fitted to the expression, X_H2O=0.20+0.0020f_H2O-0.7X_Al+0.9(X_Al)², where X_H2O is the mole fraction of H₂O (calculated with O = 1), f_H2O the fugacity of H₂O, and X_Al = Al/(Al+Si). Partial molar volume of H₂O in the melts, , calculated from the H₂O-solulbility data assuming ideal mixing of melt-H₂O solutions, is 12.5 cm³/mol for Al-free melts and decreases linearly to 8.9 cm³/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H₂O, , increases with Al/(Al+Si).Solution mechanisms of H₂O were obtained by combining Raman and ²⁹Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H₂O content. The rate of NBO/T-change with H₂O is negatively correlated with H₂O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q⁴-species to form Q² species. Steric hindrance appears to restrict bonding of H⁺ with nonbridging oxygen in Q³ species. The presence of Al³⁺ does not affect the water solution mechanisms significantly.     

Experimental determination of the diffusion coefficient for calcium in olivine between 900°C and 1500°C

Experiments have been carried out to determine the temperature, oxygen fugacity (fO₂) and compositional dependence of the tracer diffusion coefficient (D) of calcium in olivine. These data constrain the diffusion coefficient over the temperature range 900 to 1500°C for the three principal crystallographic axes. Well constrained linear relationships between the reciprocal of the absolute temperature and log(D) exist at any given oxygen fugacity. There is a strong dependence of the diffusion coefficient on oxygen fugacity with D ∝ fO₂^(1/3). This makes a knowledge of the T-fO₂ path followed by geological samples a prerequisite for modelling Ca diffusion in olivine. The best fitting preexponential factor (Do) and activation energy (E) to the Arrhenius equation log (D) = log [Do exp(−E/RT)] + 0.31Δ log fO₂ for Ca diffusion in olivine at a given oxygen fugacity (fO₂*) are given by:diffusion along [100]: log [Do (m²/s)] = −10.78 ± 0.43; E = 193 ± 11 kJ/moldiffusion along [010]: log [Do (m²/s)] = −10.46 ± 0.37; E = 201 ± 10 kJ/moldiffusion along [001]: log [Do (m²/s)] = −10.02 ± 0.29; E = 207 ± 8 kJ/molwhere Δ log fO₂ = log[fO₂*] − log[10⁻¹²] with fO₂* in units of bars. There is no measurable compositional dependence of the diffusion coefficient between Fo₈₃ and Fo₉₂. Diffusion in Fo₁₀₀ has a much higher activation energy than in Fe-bearing olivine and has a weaker fO₂ dependence.     

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

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

The effect of sulfur on the partitioning of Ni and other first-row transition elements between olivine and silicate melt

The effect of sulfur dissolved as sulfide (S²⁻) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S²⁻ were varied from zero to sulfide saturation, reaching 4100 μg g⁻¹ S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S²⁻ in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M²⁺, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S²⁻ nor of Mg#^ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S²⁻ depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10⁻³ (±1.3 × 10⁻³) K per μg g⁻¹ of S²⁻, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO₂ content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10⁻³. The ratio / is well constrained at 0.611 ± 0.016.     

Activities of NiO, FeO, and O in silicate melts

We have measured activity coefficients for NiO and FeO in a variety of silicate melts (SiO₂-CaO-MgO-Al₂O₃) using electrochemical methods similar to square wave voltametry. We report the activity of the oxide ion (a_O²⁻) in one composition. Based on these measurements, we have constructed a model that predicts the variations in activity we observe, and also variations in NiO activity reported in the literature. Activity of metal-oxide components such as NiO and FeO in silicate melts can be understood by considering contributions from both the activity of the oxide ion and the activity of the cation through expressions of the type:

     

Cohenite,native iron and troilite inclusions in garnets from polycrystalline diamond aggregates

Syngenetic garnet of eclogitic/pyroxenitic composition included in a polycrystalline diamond aggregate from the Venetia kimberlite, Limpopo Belt, South Africa shows multiple inclusions of spherules consisting of 61±5 vol% Fe₃C (cohenite), 30±2 vol% Fe-Ni and 9±3 vol% FeS (troilite). Troilite forms shells around the native iron-cohenite assemblage, implying that both compositions were immiscible melts and were trapped rapidly by the silicate. It is proposed that this polycrystalline diamond-silicate-metallic spherule assemblage formed in very local pressure and fO₂ conditions in cracks at the base of the subcratonic lithosphere from a C-H-O fluid that reacted with surrounding silicate at about 1,300–1,400 °C. In a mantle fluid consisting of CH₄>H₂O>H₂ near fO₂=IW, the H₂ activity increases rapidly when carbon from the fluid is consumed by diamond precipitation, driving the oxygen fugacity of the system to lower values along the diamond saturation curve. Water from the fluid induces melting of surrounding silicate material, and hydrogen reduces metals in the silicate melt, reflected by an unusually low Ni content of the garnet. The carbon isotopic composition of ¹³C=–13.69 (PDB) and the lack of nitrogen as an impurity is consistent with formation of the diamond from non-biogenic methane, whereas ¹⁸O=7.4 (SMOW) of the garnet implies derivation of the silicate from subduction-related material. Hence, very localized and transient reducing conditions within the subcratonic lithosphere can be created by this process and do not necessarily call for involvement of fluids derived from subducted material of biogenic origin.Editorial responsibility: J. Hoefs     

Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts

The speciation of sulfur as a function of oxygen fugacity was calculated in glasses of basaltic composition saturated experimentally with either sulfide or sulfate phases. The experiments were conducted on mixtures of synthetic and natural materials equilibrated at 1300 °C and 1 GPa in a piston-cylinder apparatus. Sulfur speciation was calculated by measuring the peak shift of the sulfur Kα radiation relative to a sulfide standard, whereas oxygen fugacity was calculated from the composition of olivine and spinel present in the assemblages. The results are consistent with sulfur being present as sulfite (S⁴⁺) in addition to sulfate (S⁶⁺) in oxidized melts. Therefore, sulfur speciation derived from SKα peak shifts should be seen as ”sulfate mole fraction equivalents“ (X(S⁶⁺)_eq.). Using the data available, an empiric function:

X(S6+)_eq.=0.86/(1+exp(2.89−2.23ΔFMQ))