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.     

Olivine/melt transition metal partitioning, melt composition, and melt structure—Influence of Al for Si substitution in the tetrahedral network of silicate melts

The influence on olivine/melt transition metal (Mn, Co, Ni) partitioning of substitution in the tetrahedral network of silicate melt structure has been examined at ambient pressure in the 1450-1550 °C temperature range. Experiments were conducted in the systems NaAlSiO₄-Mg₂SiO₄- SiO₂ and CaAl₂Si₂O₈-Mg₂SiO₄-SiO₂ with about 1 wt% each of MnO, CoO, and NiO added. These compositions were used to evaluate how, in silicate melts, substitution and ionization potential of charge-balancing cations affect activity-composition relations in silicate melts and mineral/melt partitioning.The exchange equilibrium coefficient, , is a positive and linear function of melt Al/(Al + Si) at constant degree of melt polymerization, NBO/T. The is negatively correlated with the ionic radius, r, of the M-cation and also with the ionization potential (Z/r², Z = electrical charge) of the cation that serves to charge-balance Al³⁺ in tetrahedral coordination in the melts. The activity coefficient ratio, (γ_M/γ_Mg)^melt, is therefore similarly correlated.These melt composition relationships are governed by the distribution of Al³⁺ among coexisting Q-species in the peralkaline (depolymerized) melts coexisting with olivine. This distribution controls Q-speciation abundance, which, in turn, controls (γ_M/γ_Mg)^melt and . The relations between melt structure and olivine/melt partitioning behavior lead to the suggestion that in natural magmatic systems mineral/melt partition coefficients are more dependent on melt composition and, therefore, melt structure the more alkali-rich and the more felsic the melt. Moreover, mineral/melt partition coefficients are more sensitive to melt composition the more highly charged or the smaller the ionic radius of the cation of interest.     

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.     

The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt

Experimental investigations have been performed at T = 1200°C, P = 200 MPa and fH₂ corresponding to H₂O-MnO-Mn₃O₄ and H₂O-QFM redox buffers to study the effect of H₂O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mössbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe³⁺/ΣFe ratio of the glass is directly related to aH₂O in a H₂-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H₂O ↔ H₂ + 1/2 O₂). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO₂ and Fe³⁺/Fe²⁺ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of ∼0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + ¼ O₂ = FeO_1.5). The mean centre shifts for Fe²⁺ and Fe³⁺ absorption doublets in Mössbauer spectra show little change with increasing Fe³⁺/ΣFe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses.     

Iron-bearing silicate melts: Relations between pressure and redox equilibria

Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na₂Si₂O₅-Fe₂O₃ to 40 kbar pressure at 1400° C. The Fe³⁺/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe³⁺ to Fe²⁺ and coordination transformation of remaining Fe³⁺ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.     

A possible effect of melt structure on the Mg-Fe partitioning between olivine and melt

Partitioning of Mg and Fe²⁺ between olivine and mafic melts has been determined experimentally for eight different synthetic compositions in the temperature range between 1335 and 1425°C at 0.1 MPa pressure and at fo₂ ∼1 log unit below the quartz-fayalite-magnetite buffer. The partition coefficient [K_D = (Fe²⁺/Mg)^ol/(Fe²⁺/Mg)^melt] increases from 0.25 to 0.34 with increasing depolymerization of melt (NBO/T of melt from 0.25-1.2), and then decreases with further depolymerization of melt (NBO/T from 1.2-2.8). These variations are similar to those observed in natural basalt-peridotite systems. In particular, the variation in NBO/T ranges for basaltic-picritic melts (0.4-1.5) is nearly identical to that obtained in the present experiments. Because the present experiments were carried out at constant pressure (0.1 MPa) and in a relatively small temperature range (90°C), the observed variations of Mg and Fe²⁺ partitioning between olivine and melt must depend primarily on the composition or structure of melt. Such variations of K_D may depend on the relative proportions of four-, five-, and six-coordinated Mg²⁺ and Fe²⁺ in melt as a function of degree of NBO/T.     

The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins

Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe³⁺ and Fe²⁺ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H₂O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi₂O₆, Ca_0.5AlSi₂O₆, and Mg_0.5AlSi₂O₆. Iron oxide was added in the form of Fe₂O₃, NaFeO₂, CaFe₂O₄, and MgFe₂O₄ with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe₂O₃. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe²⁺ and one of Fe³⁺. From the area ratios of the Fe²⁺ and Fe³⁺ absorption doublets, with corrections for differences in recoil-fractions of Fe³⁺ and Fe²⁺, the Fe³⁺/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe³⁺, δ_Fe³⁺, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, Δ_Fe³⁺, ranging from ∼1.2 to ∼1.6 mm/s. Both δ_Fe³⁺ and δ_Fe²⁺ are negatively correlated with total iron oxide content and Fe³⁺/ΣFe. The dominant oxygen coordination number Fe³⁺ changes from 4 to 6 with decreasing Fe³⁺/ΣFe. The distortion of the Fe³⁺-O polyhedra of the quenched melts (glasses) decreases as the Fe³⁺/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δ_Fe²⁺ and Δ_Fe²⁺ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe³⁺/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe²⁺ in a range of coordination states from 4- to 6-fold. The lower δ_Fe²⁺-values for the most oxidized melts are consistent with a larger proportion of Fe²⁺ in 4-fold coordination compared with more reduced glasses and melts.     

The Fe/ΣFe ratios of MORB glasses and their implications for mantle melting

The Fe³⁺/ΣFe ratio of 104 MORB glasses from the Pacific, the Atlantic, the Indian, and the Red Sea spreading centers have been determined using wet chemical Fe²⁺ analyses and electron microprobe FeO_total measurements. The data provide a new estimate for the MORB oxygen fugacity (fO₂) of 0.41 ± 0.43 (1sigma, N = 100) log units below the fayalite-magnetite-quartz buffer (FMQ), equivalent to a Fe³⁺/ΣFe = 0.12 ± 0.02 (1sigma, N = 104). This new fO₂ estimate is 0.8 log units more oxidized than the average fO₂ proposed by Christie et al. (1986) (FMQ-1.20 ± 0.44; Fe³⁺/ΣFe = 0.07 ± 0.01; N = 87). This slight difference may be related in part to the 3.5% underestimation of the Fe²⁺ concentration determined by Christie et al. (1986) compared with this study. MORB oxygen fugacity does not display any significant difference between the three main oceanic domains, or between enriched and depleted MORB. Yet, the iron red-ox state ratio shows a broad increase during fractional crystallization. Detailed study of magmatic suites highlights the lack of systematic Fe³⁺/ΣFe ratio fractionation during differentiation. Despite the large variations of inferred partial melting degrees (from 5 to 20%), the present data set does not provide any evidence of Fe³⁺/ΣFe relationships with partial melting proxies such as Na_8.0.Based on the Fe³⁺ systematics during partial melting, it is suggested that the oxidation state of MORB reflects a “buffered mantle melting process” resulting in the apparent compatible behavior of Fe³⁺ during partial melting, and in the relatively constant Fe³⁺/ΣFe ratio irrespective of the extent of melting. This result implies that partial melting processes may be open relative to oxygen. We propose a model where the Fe³⁺/ΣFe ratio in the melt is buffered during partial melting. The MORB Fe₂O₃ systematics can be accounted for by using a fO₂ of FMQ-1 that is equivalent to the average fO₂ reported for abyssal peridotites.     

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.     

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.     

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.     

Crystallization of melilite from CMAS-liquids and the formation of the melilite mantle of Type B1 CAIs: Experimental simulations

Type B CAIs are subdivided into B1s, with well-developed melilite mantles, and B2s, with randomly distributed melilite. Despite intensive study, the origin of the characteristic melilite mantle of the B1s remains unclear. Recently, we proposed that formation of the melilite mantle is caused by depletion of the droplet surface in volatile magnesium and silicon due to higher evaporation rates of volatile species compared to their slow diffusion rates in the melt, thus making possible crystallization of melilite at the edge of the CAI first, followed by its crystallization in the central parts at lower temperatures. Here, we present the results of an experimental study that aimed to reproduce the texture observed in natural Type B CAIs. First, we experimentally determined crystallization temperatures of melilite for three melt compositions, which, combined with literature data, allowed us to find a simple relationship between the melt composition, crystallization temperature, and composition of first crystallizing melilite. Second, we conducted a series of evaporation and cooling experiments exposing CAI-like melts to gas mixtures with different oxygen fugacities (f_O2). Cooling of the molten droplets in gases with logf_O2?IW-4 resulted in crystallization of randomly distributed melilite, while under more reducing conditions, melilite mantles have been formed. Chemical profiles through samples quenched right before melilite started to crystallize showed no chemical gradients in samples exposed to relatively oxidizing gases (logf_O2?IW-4), while the near-surface parts of the samples exposed to very reducing gases (logf_O2?IW-7) were depleted in volatile MgO and SiO₂, and enriched in refractory Al₂O₃. Using these experimental results and the fact that the evaporation rate of magnesium and silicon from CAI-like melts is proportional to , we estimate that Type B1 CAIs could be formed by evaporation of a partially molten precursor in a gas of solar composition with . Type B2 CAIs could form by slower evaporation of the same precursors in the same gas with .     

Solubility of Pt in sulphide mattes: Implications for the genesis of PGE-rich horizons in layered intrusions

The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS₂ and fO₂ at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS₂ and decreases weakly with increasing fO₂. The increase in Pt solubility with increasing fS₂ is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO₂ to the diluting effect of increasing O in the melt at high fO₂. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 10⁷ and 10¹¹, depending on fO₂ and fS₂, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 10⁷ and for the Stillwater Pt-rich horizon 10⁸. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions.     

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

     

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.     

Melt structural control on olivine/melt element partitioning of Ca and Mn

Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (K_{D Ca-Mn}^olivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum K_{D Ca-Mn}^olivine/melt-value at NBO/T near 1. Notably, published K_{D Fe2⁺-Mg}^olivine/melt versus NBO/T functions are also parabolic with a maximum in K_{D Fe2⁺-Mg}^olivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qⁿ-species) in the melt. The NBO/T-value corresponding to the minimum K_{D Ca-Mn}^olivine/melt is near that where the abundance ratio of Qⁿ-species, X_Q3/X_Q2, has its largest value. Therefore, the activity coefficient ratio in the melt, γ_Ca2⁺(melt)/γ_Mn2⁺(melt), attains a minimum where the abundance ratio of X_Q3/X_Q2 is at maximum. It is inferred from this relationship that Ca²⁺ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q³-species, whereas Mn²⁺ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qⁿ-species such as Q².     

Evidence from olivine/melt element partitioning that nonbridging oxygen in silicate melts are not equivalent

Partitioning of Ca, Mn, Mg, and Fe²⁺ between olivine and melt has been used to examine the influence of energetically nonequivalent nonbridging oxygen in silicate melts. Partitioning experiments were conducted at ambient pressure in air and 1400°C with melts in equilibrium with forsterite-rich olivine (Fo >95 mol%). The main compositional variables of the melts were NBO/T and Na/(Na+Ca). In all melts, the main structural units were of Q⁴, Q³, and Q² type with nonbridging oxygen, therefore, in the Q³ and Q² units.For melts with high Q³/Q²-abundance ratio (corresponding to NBO/T near 1), increasing Na/(Na+Ca) [and Na/(Na+Ca+Mn+Mg+Fe²⁺)] results in a systematic decrease of the partition coefficients, K_Ca^ol/melt, K_Mn^ol/melt, K_Mg^ol/melt, and K_Fe2+^ol/melt, because of ordering of the network-modifying Ca, Mn, Mg, and Fe²⁺ among nonbridging oxygen in Q³ and Q² structural units. This decrease is more pronounced the smaller the ionic radius of the cation. With decreasing Q³/Q² abundance ratio (less-polymerized melts) this effect becomes less pronounced.Activity-composition relations among network-modifying cations in silicate melts are, therefore, governed by availability of energetically nonequivalent nonbridging oxygen in individual Qⁿ-species in the melt. As a result, any composition change that enhances abundance of highly depolymerized Qⁿ-species will cause partition coefficients to decrease.     

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:

     

Experimental constraints on the mobility of Rhenium in silicate liquids

The volatization of Rhenium (Re) from melts of natural basalt, dacite and a synthetic composition in the CaO-MgO-Al₂O₃-SiO₂ system has been investigated at 0.1 MPa and 1250-1350 °C over a range of fO₂ conditions from log fO₂ = −10 to −0.68. Experiments were conducted using open top Pt crucibles doped with Re and Yb. Analysis of quenched glasses by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) normal to the melt/gas interface showed concentration profiles for Re, to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients (D). The results show Re diffusivity in basalt at 1300 °C in air is log D_Re = −7.2 ± 0.3 cm²/s and increases to log D_Re = −6.6 ± 0.3 cm²/s when trace amounts of Cl were added to the starting material. At fO₂ conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to and to in dacitic melt. In the CMAS composition, . The diffusivity of Re is comparable to Ar and CO₂ in basalt at 500 MPa favoring its release as a volatile. Our results support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts.     

Molybdenum, tungsten and manganese partitioning in the system pyrrhotite-Fe-S-O melt-rhyolite melt: Impact of sulfide segregation on arc magma evolution

Experiments were performed to determine the partitioning of molybdenum, tungsten and manganese among a rhyolitic melt (melt), pyrrhotite (po), and an immiscible Fe-S-O melt (Fe-S-O). Sulfide phases such as these may be isolated from a silicate melt along with other crystallizing phases during the evolution of arc magma, and partition coefficients are required to model the effect of this process on molybdenum and tungsten budgets.We developed an experimental design to take advantage of properties of the phases under study. Careful control of temperature allowed pyrrhotite and magnetite to be stable along with an Fe-S-O melt, and this phase assemblage allowed the composition of run-product pyrrhotite to be used to calculate both fS₂ and fO₂ for the experiments. At run temperature, (1042 ± 2 °C), a rhyolitic melt can be formed at low pressure, under nominally dry conditions, which removed the need for confining pressure as well as externally imposed fugacities. The silica-saturated melt allowed the charges to be contained in sealed evacuated silica tubes without danger of reaction, and with closed system behavior for molybdenum and tungsten.Experiments were run for durations up to 2000 min. Molybdenite (mb) and wolframite (wo) were added to the experiments as sources for molybdenum and tungsten, respectively. Manganese was added to the system as both a component of the starting rhyolitic pumice, and of Mn-bearing wolframite. Oxygen fugacity in these experiments was fixed at the Ni-NiO oxygen fugacity buffer. Sulfur fugacity was 10⁻¹ bar. Run products were analyzed by EPMA and LA-ICP-MS. Analysis of the run products yielded ( standard deviation of the mean): , , , and . The partition coefficients for manganese in this system are and .Simple Rayleigh fractionation modeling suggests that oxidized felsic melts produced through fractional crystallization may have lost as much as 14% of their initial molybdenum, but only 2% of their initial tungsten, through the removal of an Fe-S-O melt along with crystalline phases. Modeling consistent with conditions of oxygen and sulfur fugacity influenced by assimilation of sulfide (with low concentrations of molybdenum and tungsten) from, for example, sedimentary rock, results in evolved magmas significantly depleted in molybdenum, but only moderately depleted in tungsten. The molybdenum:tungsten ratio can vary by two orders of magnitude. These systematics may help to explain some of the variability in metal ratios of intrusion-related hydrothermal ore deposits.