The effect of oxygen fugacity on the partitioning of Re between crystals and silicate melt during mantle melting

Interpretation of Re-Os isotopic systematics applied to mantle and mantle-derived rocks is currently hindered by the poorly understood behaviour of Re and Os during partial melting. Of particular interest is the incompatibility of Re and how it partitions between melt and the different mantle phases. Here, we study the partitioning behaviour of Re between the common upper mantle minerals (garnet, spinel, clinopyroxene, orthopyroxene, and olivine) and silicate melt under temperature (1275-1450 °C) and pressure (1.5-3.2 GPa) conditions relevant for basaltic magma genesis, over a range of oxygen fugacity (?O₂) large enough (QFM+5.6 to QFM−2.9) to demonstrate the effects of changing the oxidation state of Re from 4+ to 6+. Rhenium crystal/silicate-melt partition coefficients vary by 4-5 orders of magnitude, from moderately compatible to highly incompatible, for pyroxenes, garnet, and spinel as the oxidation state of Re changes from 4+ to 6+, but Re in either oxidation state is incompatible in olivine. Because the changeover from the one Re oxidation state to the other occurs over the range of ?O₂s pertinent to partial melting in the Earth’s mantle, bulk Re crystal/silicate-melt partition coefficients during mantle melting are also expected to vary significantly according to the oxidation state of the system. For instance, assuming QFM−0.7 and QFM+1.6 as average ?O₂ for mid-ocean ridge (MORBs) and island arc (IABs) basalts, respectively, a difference of at least one order of magnitude for bulk Re partition coefficients is expected (excluding any influence from a sulphide phase). Hence, Re is probably much more incompatible during the genesis of IABs compared to MORBs. Our results also demonstrate that Re⁴⁺ has a partitioning behaviour similar to Ti⁴⁺ rather than Yb, and is accordingly not a sensitive indicator of garnet in the source. The lower concentrations of Re observed in ocean island basalts (OIBs) compared to MORBs are therefore not a result of being generated deeper in the mantle where garnet is stable, leaving the hypothesis of late-stage loss of Re from OIB lavas by degassing as the most plausible explanation.     

Partitioning of ferric and ferrous iron between plagioclase and silicate melt

Using the thermodynamic algorithm of Sugawara (Contributions to Mineralogy and Petrology 141, 2001, p. 659–686), FeO and Fe₂O₃ concentrations in plagioclase were computed for 420 published experiments on tholeiitic, FeTi-tholeiite, calc-alkaline, and alkaline magma compositions. Estimates of the partition coefficient between plagioclase and liquid range from 0.19 to 0.92 for Fe₂O₃ and from 0.008 to 0.050 for FeO, i.e. ca. twenty times greater for Fe₂O₃ than for FeO. Partitioning of Fe₂O₃ and FeO is independent of both oxygen fugacity and plagioclase composition, contradicting the common assumption that partitioning of Fe₂O₃ correlates positively with the amount of aluminium in plagioclase. In contrast, the SiO₂-content of the magma correlates positively with the partition coefficients for Fe₂O₃ and FeO. This is ascribed to increasing activity of iron in polymerised SiO₂-rich magma. Advances of micro-beam Fe-XANES techniques allow the determination of Fe³⁺/Fe in plagioclase. Using such plagioclase data and the partition coefficients for Fe₂O₃ and FeO, the Fe₂O₃/FeO and oxygen fugacity of equilibrium magma may be estimated. As petrological examples, we estimate that the oxygen fugacity of the Palisades sill ranged from the QFM buffer to 0.5 log unit below it (QFM to QFM –0.5), the Lake County basalt from QFM to QFM –2, and Upper Zone a of the Skaergaard intrusion from QFM –1 to QFM –1.5.Editorial responsibility: I. Parsons     

The oxidation state of europium as an indicator of oxygen fugacity

The distribution of Eu between plagioclase feldspar and magmatic liquid has been determined experimentally for basaltic and andesitic systems as a function of temperature and oxygen fugacity at one atmosphere total pressure. Using the approach of Philpotts the ratios $\text{Eu}{}^{\mathrm{2+}}\text{Eu}{}^{\mathrm{3+}}$ in plagioclase and coexisting magmatic liquid have been calculated. These ratios appear to be simply related to oxygen fugacity for the bulk compositions studied here. Using published trace element distribution data for natural rocks oxygen fugacities may be calculated from these experimental results. For terrestrial basalts calculated oxygen fugacities average 10^?7 with little dispersion from this value. Andesites average 10^?8.1 with considerable dispersion, while dacites and rhyodacites average 10^?9.1, also with considerable dispersion. Oxygen fugacities for lunar ferrobasalts cluster tightly around 10^?12.7. Data on achondritic meteorites are limited, but calculations indicate oxygen fugacities of two-to-five orders of magnitude lower than lunar ferrobasalts.     

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.     

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO₂-Al₂O₃-Fe₂O₃-FeO-MgO-CaO-Na₂O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe³⁺,Al³⁺)Si₂O₈-Ca(Fe²⁺,Mg)Si₃O₈ system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeO^t, MgO content and Mg/(Fe^t+Mg) in plagioclase can be predicted from liquid composition with standard deviations of ǂ.34 wt% (relative error =9%) and ǂ.08 wt% (14%) and ǂ.7 (8%) respectively. Calculated Fe³⁺-Al exchange chemical potentials of plagioclase, m_{Fe^{3 +} ( Al )- 1} ^Pl{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Pl}} agree with those calculated using reported thermodynamic models for multicomponent spinel, m_{Fe^{3 +} ( Al )- 1} ^Sp{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Sp}} and clinopyroxene, m_{Fe^{3 +} ( Al )- 1} ^Cpx{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Cpx}} . The FeO^t content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe³⁺/(Fe³⁺+Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and f_O2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.     

An experimental study of rare earth element partitioning between a shergottite melt and pigeonite: implications for the oxygen fugacity of the mart ian interior

A series of experiments on a synthetic, pigeonite-saturated, basaltic shergottite were carried out to constrain the variation of D(Eu/Gd)_{pigeonite/melt} and D(Eu/Sm)_{pigeonite/melt} with oxygen fugacity (f_O2). The experiments have been run under both dry and hydrous conditions. The shergottite was doped with 0.1, 0.5, and 1.0 wt.% Eu, Gd, and Sm oxides in different experiments and was equilibrated at liquidus conditions for 24 hours. D(Eu/Gd)_{pigeonite/melt} in dry melts ranges from 0.156 ± 0.014 (f_O2 = IW − 1) to 0.630 ± 0.102 (IW + 3.5). D(Eu/Sm)_{pigeonite/melt} in dry melts ranges from 0.279 ± 0.021 (IW − 1) to 1.114 ± 0.072 (IW + 3.5). Due to difficulties with low-f_O2 experiments, hydrous distribution coefficients were measured, but were not used in the calibration of the Eu-oxybarometers. These two Eu-oxybarometers provide an accurate way to measure f_O2 recorded during pigeonite crystallization, thereby yielding a record of f_O2 during the earliest period of Martian meteorite parent magma crystallization history.Using this new calibration, Martian meteorite pigeonite cores record f_O2 values of IW − 0.6 (±0.3) (QUE94201) to IW + 1.9 (±0.6) (Shergotty). These new values differ in magnitude, but not trend, from previously published data. The pigeonite Eu-oxybarometer yields an f_O2 range in the basaltic shergottites of 2 to 3 orders of magnitude. Several processes have been proposed to explain the origin of this f_O2 range, the majority of which rely on assimilation of an oxidized source. A potential correlation between this new pigeonite data and recent Fe-Ti oxide data, however, is consistent with intrinsic f_O2 differences in the magma source region being responsible for the measured f_O2 variations. This implies that the Martian meteorite source region, the mantle or lithosphere, may be heterogeneous in nature. However, the process of assimilation cannot be completely ruled out in that an assimilation event that took place before crystallization commenced would result in the overprinting of the source region f_O2 signature.     

Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt

The influence of oxygen fugacity and water on phase equilibria and the link between redox conditions and water activity were investigated experimentally using a primitive tholeiitic basalt composition relevant to the ocean crust. The crystallization experiments were performed in internally heated pressure vessels at 200 MPa in the temperature range 940–1,220°C. The oxygen fugacity was measured using the H₂-membrane technique. To study the effect of oxygen fugacity, three sets of experiments with different hydrogen fugacities were performed, showing systematic effects on the phase relations and compositions. In each experimental series, the water content of the system was varied from nominally dry to water-saturated conditions, causing a range of oxygen fugacities varying by ~3 log units per series. The range in oxygen fugacity investigated spans ~7 log units. Systematic effects of oxygen fugacity on the stability and composition of the mafic silicate phases, Cr–spinel and Fe–Ti oxides, under varying water contents were recorded. The Mg# of the melt, and therefore also the Mg# of olivine and clinopyroxene, changed systematically as a function of oxygen fugacity. An example of the link between oxygen fugacity and water activity under hydrogen-buffered conditions is the change in the crystallization sequence (olivine and Cr–spinel) due to a change in the oxygen fugacity caused by an increase in the water activity. The stability of magnetite is restricted to highly oxidizing conditions. The absence of magnetite in most of the experiments allows the determination of differentiation trends as a function of oxygen fugacity and water content, demonstrating that in an oxide-free crystallization sequence, water systematically affects the differentiation trend, while oxygen fugacity seems to have a negligible effect.     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 1. Experimental results and the investigation of controls on partitioning behaviour

Thirty five minor and trace elements (Li, Be, B, Sc, Cu, Zn, Ga, Ge, As, Rb, Nb, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Nd, Sm, Tb, Ho, Tm, Lu, Hf, Ta, W, Tl, Pb, Bi, Th and U) in experimentally produced near-liquidus phases, from a primitive nelpheline basanite from Bow Hill in Tasmania (Australia), were analysed by LAM ICP-MS. A number of halogens (F, Cl and I) were also analysed by electron microprobe. The analyses were used to determine mineral/melt partition coefficients for mica, amphibole, garnet, clinopyroxene, orthopyroxene and olivine for conditions close to multiple saturation of the basanite liquidus with garnet lherzolite (approximately 2.6 GPa and 1,200°C with 7.5 wt% of added H₂O). A broader range of conditions was also investigated from 1.0 GPa and 1,025°C to 3.5 GPa and 1,190°C with 5–10 wt% of added H₂O. The scope and comprehensiveness of the data allow them to be used for two purposes, these include the following: an investigation of some of the controlling influences on partition coefficients; and the compilation of a set partition coefficients that are directly relevant to the formation of the Bow Hill basanite magma by partial melting of mantle peridotite. Considering clinopyroxene, the mineral phase for which the most data were obtained, systematic correlations were found between pressure and temperature, mineral composition, cation radius and valence, and ΔG ^coulb (the coulombic potential energy produced by substituting a cation of mismatched valence into a crystallographic site). ΔG ^coulb is distinctly different for different crystallographic sites, including the M2 and M1 sites in clinopyroxene. These differences can be modelled as a function of variations in optimum valence (expressed as 1 sigma standard deviations) within individual M1 and M2 site populations.     

Effect of oxygen fugacity on the etching rate of diamond crystals in silicate melt

Experimental data on the etching of diamond crystals in basaltic melt at 1130°C with variable oxygen fugacity in the environment are considered. The oxygen fugacity was set with the HM and NNO buffers. The study was carried out on a 0.6–0.8 mm fraction (powder) of natural diamond crystals. It has been established that, at the same temperature, the rate of diamond etching (oxidation) in silicate melt depends on the oxygen fugacity in the environment. The etching rate decreases with decline in the oxygen fugacity from the case where the melt comes into contact with atmospheric air to the conditions controlled by the HM and NNO buffers. Under the conditions of the HM and NNO buffers, oxidation was accompanied by surface graphitization of diamond crystals.     

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH.     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.     

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.     

Fe–Mg partitioning between ringwoodite and magnesiowüstite and the effect of pressure, temperature and oxygen fugacity

 The partitioning of Mg and Fe between magnesiowüstite and ringwoodite solid solutions has been measured between 15 and 23 GPa and 1200–1600 ^∘C using both Fe and Re capsule materials to vary the oxidation conditions. The partitioning results show a clear dependence on the capsule material used due to the variation in Fe³⁺ concentrations as a consequence of the different oxidation environments. Using results from experiments performed in Fe capsules, where metallic Fe was also added to the starting materials, the difference in the interaction parameters for the two solid solutions (W _FeMg ^mw−W _FeMg ^ring) is calculated to be 8.5±1 kJ mol⁻¹. Similar experiments performed in Re metal capsules result in a value for W _FeMg ^mw−W _FeMg ^ring that is apparently 4 kJ higher, if all Fe is assumed to be FeO. Electron energy-loss near-edge structure (ELNES) spectroscopic analyses, however, show Fe³⁺ concentrations to be approximately three times higher in magnesiowüstite produced in Re capsules than in Fe capsules and that Fe³⁺ partitions preferentially into magnesiowüstite, with K _{D Fe3+} ^ring/mw estimated between 0.1 and 0.6. Using an existing activity composition model for magnesiowüstite, a least–squares fit to the partitioning data collected in Fe capsules results in a value for the ringwoodite interaction parameter (W _FeMg ^ring) of 3.5±1 kJ mol⁻¹. The equivalent regular interaction parameter for magnesiowüstite (W _FeMg ^mw) is 12.1±1.8 kJ mol. These determinations take into account the Fe³⁺ concentrations that occur in both phases in the presence of metallic Fe. The free energy change in J mol⁻¹ for the Fe exchange reaction can be described, over the range of experimental conditions, by 912 + 4.15 (T−298)+18.9P with T in K, P in kbar. The estimated volume change for this reaction is smaller than that predicted using current compilations of equation of state data and is much closer to the volume change at ambient conditions. These results are therefore a useful test of high pressure and temperature equation of state data. Using thermodynamic data consistent with this study the reaction of ringwoodite to form magnesiowüstite and stishovite is calculated from the data collected using Fe capsules. Comparison of these results with previous studies shows that the presence of Fe³⁺ in phases produced in multianvil experiments using Re capsules can have a marked effect on apparent phase relations and determined thermodynamic properties. Received: 13 September 2000 / Accepted: 25 March 2001     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

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

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

Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

A long-duration experiment on hydrous species geospeedometer and hydrous melt viscosity

A 2.4-year controlled-cooling-rate experiment was carried out to investigate the dependence of hydrous species concentrations in rhyolitic melt on cooling rate. The experiment allows us to obtain speciation for a cooling rate of 1.68 × 10⁻⁶ K/s, extending previous experimental data by two orders of magnitude. Furthermore, a viscosity as high as 10^17.2 Pa s is inferred for this hydrous rhyolitic melt with 0.85 wt% total H₂O at 671 K. The results are applied to examine whether a geospeedometry model and four viscosity models may be extrapolated to slower cooling rates or lower temperatures. Two of the viscosity models and the geospeedometry model can be extrapolated by two orders of magnitude upwards in terms of viscosity or downwards in terms of cooling rate.