The distribution of Fe and Mg between olivine and lunar basaltic liquids

We have examined the Fe and Mg distribution between coexisting olivine and lunar basaltic liquids produced by equilibrium partial melting of natural lunar samples. In agreement with the findings of Roeder and Emslie (Contrib. Mineral. Petrol. 29, 275–289) on terrestrial compositions, the logarithms of the conventional distribution coefficients, K_ol-L^Fe and K_ol-L^Fe-Mg, are nearly linear functions of inverse temperature; and the exchange coefficient, K_D = K_ol-L^Fe-Mg, is nearly independent of temperature and composition within a given magma group. There are, however, small but significant differences in conventional and exchange distribution coefficients from one magma group to another, e.g. low-Ti vs high-Ti lunar basalts. It is possible to achieve slightly greater precision for the inverse temperature functions by including terms approximating silica activity in the conventional distribution coefficients. The term ($\text{2Si}\text{O}\text{)}{}_{\mathrm{L}}$ is apparently the best simple approximation for silica activity in olivine-saturated liquids based upon data for Fe, Mg, Mn, Ca, Ti and Cr. Pressure has noticeable effects upon Fe and Mg distribution between olivine and liquid only above 5 kbar.The excellent linear correlation of the logarithms of the distribution coefficients with inverse temperature allows calculation of approximate values of $\text{Δ}\text{H}\text{?}{}^0$ for the reactions : 2MgO_L + SiO_2LaiMg₂SiO_4ol and 2FeO_L + SiO_2LaiFe₂SiO_4ol. Values obtained, approx ?26 kcal/mole, are comparable with values of the heats of fusion of forsterite and fayalite calculated by Bradley (Am. J. Sci.260, 550–554) and measured by Orr (J. Am. Chem. Soc. 75, 528–529).The exchange distribution coefficient for Fe and Mg, K_D, is sensitive to large changes in liquid chemistry. Although K_D is explicitly independent of silica activity, K_D apparently changes with silica concentration. This change is a reflection of changes in the mixing properties of Fe and Mg in liquids with different chemistry and hence structure. Regular solution theory predicts that as the mixing properties of an element in a solution change, the most radical changes in activity coefficients occur in the range of dilute concentrations. Therefore, the distribution coefficients for trace elements will also be dependent upon large changes in liquid chemistry, even if corrections for silica and other liquid component activities are applied.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

Element partitioning between olivine and silicate melt under high pressure

Element partitioning between olivine and silicate melt has been investigated at pressures 1–14 GPa, by using a 6–8 type multi-anvil high pressure apparatus. In order to observe systematics in the partitioning of trivalent ions, Li was added to the starting materials in order to increase the concentration of trivalent ions in olivine. With increasing pressure, it was found that partition coefficients of most of the elements gradually decreased. Trivalent ions generally showed parabolic pattern on partition coefficient — ionic radius diagram. When pyrolite-like material was used as the starting material, partition coefficient of Al, D_Al, gradually increased with increase in pressure while the partition coefficients of the other elements decreased, and the D_Al deviated from the parabolic pattern of other trivalent ions. The deviation of D_Al from the D pattern of the other trivalent ions was also found when olivine was employed as main component of the starting material. This result may be ascribed to the compositional change of coexisting silicate melt with increase in pressure.     

Experimental calibration of the partitioning of Fe and Mg between biotite and garnet

The cation exchange reaction Fe₃Al₂Si₃O₁₂ +KMg₃AlSi₃O₁₀(OH)₂ = Mg₃Al₂Si₃O₁₂+KFe₃-AlSi₃ O₁₀(OH)₂ has been investigated by determining the partitioning of Fe and Mg between synthetic garnet, (Fe, Mg)₃Al₂Si₃O₁₂, and synthetic biotite, K(Fe, Mg)₃AlSi₃O₁₀(OH)₂. Experimental results at 2.07 kbar and 550 °–800 ° C are consistent with In [(Mg/Fe) garnet/(Mg/Fe) biotite] = -2109/T(°K) +0.782. The preferred estimates for ¯H and ¯S of the exchange reaction are 12,454 cal and 4.662 e.u., respectively. Mixtures of garnet and biotite in which the ratio garnet/biotite=49/1 were used in the cation exchange experiments. Consequently the composition of garnet-biotite pairs could approach equilibrium values in the experiments with minimal change in garnet composition (few tenths of a mole percent). Equilibrium was demonstrated at each temperature by reversal of the exchange reaction. Numerical analysis of the experimental data yields a geothermometer for rocks containing biotite and garnet that are close to binary Fe-Mg compounds.     

The behavior of Mg, Fe, and Ni during the replacement of olivine by orthopyroxene: experiments relevant to mantle metasomatism

Replacement of olivine by orthopyroxene is a frequently observed phenomenon in mantle metasomatism. In order to study element redistribution in SiO₂ metasomatism we synthesised orthopyroxene reaction rims at the contacts between forsterite-rich olivine and quartz. The orthopyroxene rims grew from the original quartz-olivine interface into both directions implying counterdiffusion of iron/magnesium and silicon. Following local equilibrium partitioning the X_Fe is lower in the orthopyroxene than in the reactant olivine at the olivine-orthopyroxene replacement front. The resulting local iron excess is compensated by formation of orthopyroxene with a higher X_Fe at the quartz-orthopyroxene interface, which is out of equilibrium with the reactant olivine. This is facilitated through short circuit diffusion along grain boundaries within the orthopyroxene rim. Due to the low capacity of orthopyroxene to accommodate Ni, this component is forced to diffuse back into the olivine producing a Ni enriched zone ahead of the replacement front. This leads to Ni contents in the orthopyroxene rim, which are higher than what is expected in equilibrium with the unaltered olivine. Taking quartz as a proxy for a silica rich fluid or liquid metasomatising agent, we conclude that the overall element fractionation between olivine and the silica rich phase may deviate from equilibrium partitioning so that the Fe and Ni concentrations in the orthopyroxene which is in contact with quartz are higher than in equilibrium with the reactant olivine. This indicates that kinetic fractionation is important for the chemical evolution of both the mantle rocks and the metasomatising agents.     

Thermodynamic analysis of Fe and Mg partitioning between plagioclase and silicate liquid

 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl₂Si₂O₈-CaFeSi₃O₈ and CaAl₂Si₂O₈-CaMgSi₃O₈. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe³⁺ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe³⁺/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X _Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X _Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999     

An experimental study of the partitioning of Fe and Mg between garnet and orthopyroxene

The partitioning of Fe and Mg between garnet and aluminous orthopyroxene has been experimentally investigated in the pressure-temperature range 5–30 kbar and 800–1,200° C in the FeO-MgO-Al₂O₃-SiO₂ (FMAS) and CaO-FeO-MgO-Al₂O₃-SiO₂ (CFMAS) systems. Within the errors of the experimental data, orthopyroxene can be regarded as macroscopically ideal. The effects of Calcium on Fe-Mg partitioning between garnet and orthopyroxene can be attributed to non-ideal Ca-Mg interactions in the garnet, described by the interaction term:W _CaMg ^ga -W _CaFe ^ga =1,400±500 cal/mol site. Reduction of the experimental data, combined with molar volume data for the end-member phases, permits the calibration of a geothermometer which is applicable to garnet peridotites and granulites: $$T(^\circ C) = \left\{ {\frac{{3,740 + 1,400X_{gr}^{ga} + 22.86P(kb)}}{{R\ln K_D + 1.96}}} \right\} - 273$$ with $$K_D = {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } \mathord{\left/ {\vphantom {{\left\{ {\frac{{Fe}}{{Mg}}} \right\}^{ga} } {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}} \right. \kern-\nulldelimiterspace} {\left\{ {\frac{{Fe}}{{Mg}}} \right\}}}$$ and $$X_{gr}^{ga} = (Ca/Ca + Mg + Fe)^{ga} .$$ The accuracy and precision of this geothermometer are limited by largerelative errors in the experimental and natural-rock data and by the modest absolute variation inK _D with temperature. Nevertheless, the geothermometer is shown to yield reasonable temperature estimates for a variety of natural samples.     

Effect of grossular-content in garnet on the partitioning of Fe and Mg between garnet and biotite

In contrast to Ferry (1980) (X _Ca)-values in garnet even lower than 0.1 have a significant effect on the calculated equilibrium temperature using the experimental calibration of the Fe and Mg paritioning between garnet and biotite. Garnet compositions and Mg/Fe — distribution coefficients from samples of the Eoalpine staurolite — in zone in the southern Ötztal are related by the quadratic regression equation: InK _D= -1.7500 (±0.0226) + 2.978 (±0.5317)X _Ca ^Gt -5.906(±2.359)(X _Ca ^Gt )² Temperatures derived by the Ferry and Spear (1978) calibration using chemistry — correctedK _D values are petrologically realistic.Analysis of our data supports non ideal mixing of grossular with almandine — pyrope solid solution. The derived excess mixing energies are quite small for the almandine — pyrope solution (W _FeMg= –133 cal/mole) and about +2775 cal/mole for the difference between pyrope-grossular and almandine-grossular solutions (W _MgCa —W _FeCa) at metamorphic conditions of 570° C and 5,000 bar. The mixing parameters proposed by Ganguly and Saxena (1984) are not confirmed by our data as they would result in significantly lower temperatures.     

The electrical conductivity of olivine under highly reducing conditions

The electrical conductivity of San Carlos olivine has been measured at 1100 °C under reducing conditions at controlled oxygen fugacity, inside and outside the olivine stability field, in order to study the kinetics of olivine destabilization. Electrical conductivity increases along the direction [010] and decreases along [001]. as oxygen fugacity decreases. To understand these dependences, electrical conductivity transitory regimes were studied. In response to decreases in oxygen fugacity, two transient regimes with different time scales have been observed. A fast (≈1–2 min) increase of electrical conductivity is first observed, followed by a slower decrease (1–10 h, depending on the crystal orientation). After a few hours of annealing, precipitation of metallic iron and nickel and formation of amorphous silica can be observed at the crystal surface. The fast conductivity increase in the first transient regime is ascribed to an increase in the population of electrons at the olivine surface. Two effects: (1) equilibration of surface defects with the bulk of the crystal, and (2) iron loss from the olivine due to metal precipitation, could explain the subsequent decrease of electrical conductivity. Anisotropic diffusion of surface defects to the bulk of the crystal, by a process faster than atomic diffusion is the most likely. Received: 3 September 1997 / Revised, accepted: 16 April 1998     

Mg-Fe partitioning between olivine and ultramafic melts at high pressures

Precise determination of the partitioning of Mg and Fe²⁺ between olivine and ultramafic melt has been made at pressures from 5 to 13 GPa using a MA-8 type multi-anvil high-pressure apparatus (PREM) installed at Earthquake Research Institute, University of Tokyo. A very short rhenium capsule (<100 μm sample thickness) was adopted to minimize temperature variation within the sample container. Synthetic gels with the composition of the upper mantle peridotite were used as starting materials to promote the homogeneity. Analyses of quenched melts and coexisting olivines were made with an electron probe microanalyzer. The obtained partition coefficient, K_D [=(FeO/MgO)^ol/(FeO/MgO)^melt], decreases from 0.35 to 0.25 with increasing pressure from 5 to 13 GPa, suggesting a negative correlation between pressure and K_D above 5 GPa. Our result is consistent with a parabolic relationship between K_D and degree of polymerization (NBO/T) of melts reported by previous studies at lower pressures. The negative correlation between pressure and K_D suggests that olivine crystallizing in a magma ocean becomes more Mg-rich with depth and that primary magmas generated in the upper mantle become more Fe-rich with depth than previously estimated.     

The effect of liquid composition on the partitioning of Ni between olivine and silicate melt

We report the results of experiments designed to separate the effects of temperature and pressure from liquid composition on the partitioning of Ni between olivine and liquid, \(D_{\text{Ni}}^{\text{ol/liq}}\). Experiments were performed from 1300 to 1600 °C and 1 atm to 3.0 GPa, using mid-ocean ridge basalt (MORB) glass surrounded by powdered olivine in graphite–Pt double capsules at high pressure and powdered MORB in crucibles fabricated from single crystals of San Carlos olivine at one atmosphere. In these experiments, pressure and temperature were varied in such a way that we produced a series of liquids, each with an approximately constant composition (~12, ~15, and ~21 wt% MgO). Previously, we used a similar approach to show that \(D_{\text{Ni}}^{\text{ol/liq}}\) for a liquid with ~18 wt% MgO is a strong function of temperature. Combining the new data presented here with our previous results allows us to separate the effects of temperature from composition. We fit our data based on a Ni–Mg exchange reaction, which yields \(\ln \left( {D_{\text{Ni}}^{\text{molar}} } \right) = \frac{{ -\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{RT} + \frac{{\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{R} - \ln \left( {\frac{{X_{\text{MgO}}^{\text{liq}} }}{{X_{{{\text{MgSi}}_{ 0. 5} {\text{O}}_{ 2} }}^{\text{ol}} }}} \right).\) Each subset of constant composition experiments displays roughly the same temperature dependence of \(D_{\text{Ni}}^{\text{ol/liq}}\) (i.e.,\(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\)) as previously reported for liquids with ~18 wt% MgO. Fitting new data presented here (15 experiments) in conjunction with our 13 previously published experiments (those with ~18 wt% MgO in the silicate liquid) to the above expression gives \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 3641 ± 396 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 1.597 ± 0.229. Adding data from the literature yields \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 4505 ± 196 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 2.075 ± 0.120, a set of coefficients that leads to a predictive equation for \(D_{\text{Ni}}^{\text{ol/liq}}\) applicable to a wide range of melt compositions. We use the results of our work to model the melting of peridotite beneath lithosphere of varying thickness and show that: (1) a positive correlation between NiO in magnesian olivine phenocrysts and lithospheric thickness is expected given a temperature-dependent \(D_{\text{Ni}}^{\text{ol/liq}} ,\) and (2) the magnitude of the slope for natural samples is consistent with our experimentally determined temperature dependence. Alternative processes to generate the positive correlation between NiO in magnesian olivines and lithospheric thickness, such as the melting of olivine-free pyroxenite, are possible, but they are not required to explain the observed correlation of NiO concentration in initially crystallizing olivine with lithospheric thickness.     

The stability and major element partitioning of ilmenite and armalcolite during lunar cumulate mantle overturn

Ilmenite has played an important role in the petrogenesis of lunar high-Ti picritic magmas, and armalcolite is another high-Ti oxide that was first discovered on the moon. In this study, we examined the thermodynamic stability of ilmenite and armalcolite in the context of lunar cumulate mantle overturn. Two starting compositions were explored, an ilmenite-bearing dunite (olivine + ilmenite) and an ilmenite-bearing harzburgite (olivine + orthopyroxene + ilmenite). Experiments were conducted using a 19.05 mm piston-cylinder apparatus at temperatures of 1235-1475 °C and pressures of 1-2 GPa. In runs with the ilmenite-bearing dunite mixture, ilmenite is stable in the subsolidus assemblage at least up to 1450 °C and 2 GPa. In runs with the ilmenite-bearing harzburgite starting mixture, ilmenite is stable at pressures greater than 1.4 GPa, and armalcolite is stable at lower pressures. Solidi for both starting compositions were determined, and the phase boundary between ilmenite- and armalcolite-bearing harzburgite was shown to have little dependence on temperature. During lunar cumulate overturn, sinking ilmenite formed near the end of lunar magma ocean solidification transforms into armalcolite when in contact with harzburgite cumulates at depths of less than 280 km in the lunar mantle. Inefficient overturn could leave isolated, inhomogeneously distributed pockets of armalcolite-bearing harzburgite in the upper lunar mantle, underlain by an ilmenite-bearing lower lunar mantle. These high-Ti oxide-bearing harzburgitic pockets can serve as potential sources for the generation of high-Ti magmas through partial melting or through assimilation of high-Ti minerals during transport of low-Ti picritic magmas in the lunar mantle.FeO-MgO exchange between olivine and either ilmenite or armalcolite was also examined in this study. We found the FeO-MgO distribution coefficient to be effectively independent of temperature for the pressures, temperatures, and compositions explored, with an average value of 0.179 ± 0.008 for olivine/ilmenite and 0.319 ± 0.021 for olivine/armalcolite. Given the bulk composition of an overturned lunar cumulate mantle, our measured FeO-MgO distribution coefficients can be used to estimate the Mg# of coexisting minerals in armalcolite- or ilmenite-bearing harzburgite and dunite in the overturned lunar mantle. Finally, the transformation from ilmenite-bearing harzburgite to armalcolite-bearing harzburgite results in a density increase of up to 2%. Large armalcolite-bearing cumulate bodies in the upper lunar mantle may be detectable in future lunar geophysical experiments.     

Aluminum partitioning between olivine and ultrabasic silicate liquid to 6 GPa

Trace element analyses of 1-atm and high-pressure experiments show that in komatiite and peridotite, the olivine (OL)/liquid (L) distribution coefficient for Al₂O₃ ( ) increases with pressure and temperature. Olivine in equilibrium with liquid accepts as much as 0.2 wt% Al₂O₃ in solution at 6 GPa. Convergence to equilibrium compositions at this high level is shown by cation diffusion of Al into synthetic forsterite crystals of low-Al contents in the presence of melt. Convergence to low-Al equilibrium compositions at lower P and T is shown by diffusion of Al out of synthetic forsterite with high initial Al content. Isobaric and isothermal experimental data subsets reveal that temperature and pressure variations both have real effects on . Variation in silicate melt composition has no detectable effect on within the limited range of experimentally investigated mixtures. Least-squares regression for 24 experiments, using komatiite and peridotite, performed at 1 atm to 6 GPa and 1300 to 1960°C, gives the best fit equation: Increase in with increasingly higher-pressure melting is consistent with incorporation of a spinel-like component of low molar volume into olivine, although other substitutions possibly involving more complex coupling cannot be ruled out. High P-T ultrabasic melting residues, if pristine, may be recognized by the high calculated from microprobe analyses of Al₂O₃ concentrations in residual olivines and estimated Al₂O₃ concentration in the last liquid removed. In general the low levels of Al in natural olivine from mantle xenoliths suggest that pristine residues are rarely recovered.     

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     

Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism

Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO₂-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO₂ at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000     

Infrared spectroscopic investigation of hydroxyl in β-(Mg,Fe)2SiO4 and coexisting olivine: Implications for mantle evolution and dynamics

Wadsleyite (β-(Mg,Fe)₂SiO₄) is a major constituent of the Earth's transition zone and is known to accommodate OH. The portion of the transition zone between 400–550 km could be an important source or sink for hydroxyl in plumes and slabs intersecting this region. Micro-infrared spectroscopy has been carried out on the β-phase and coexisting metastable olivine synthesized in a multianvil apparatus at 14 GPa and 1550–1650 K under hydrous conditions. Single-crystal and polycrystal specimens of both phases were analyzed in the 1800–8500 cm^?1 frequency region to determine the speciation, abundances, and partitioning behavior of the hydrous components in coexisting β-phase and olivine. β-phase spectra consistently show three distinct OH bands at 3329, 3580, and 3615 cm^?1. OH concentrations range from 10000–65000 H/10⁶ Si. A strong positive correlation of grain size and extent of transformation with OH concentration in the β-phase indicates that grain-growth and transformation rates are enhanced in a hydrous environment. Olivine spectra are variable, but consistently show a prominent broad-band absorbance representing molecular H₂O, consistent with the infrared signature of the starting material. OH concentrations in olivine range from <300–1400 H/10⁶ Si. The highest OH concentrations measured for olivine and the β-phase may represent solubility limits, in which case the OH solubility ratio between these two phases is approximately 1∶40. Where both phases coexist and are undersaturated with OH, the partitioning ratio of OH between them is about 1∶100. The large solubility contrast between olivine and the β-phase suggests a mechanism for hydrating the transition zone via olivine carried down in subducting slabs. Plumes impinging on an OH-rich upper transition region could cause H₂ or H₂O to be released upon transformation of the β-phase to olivine, resulting in initiation of secondary upwellings. If dissolution of OH weakens the β-phase, and if OH is present in the mantle, the region between 400–550 km could be a zone of low viscosity.     

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth’s mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280?°C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F–Cl–Br–I–H₂O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H₂O (D_Cl ^ol/melt = 1.6?±?0.9 × 10^?4) to 0.33 (6) wt% H₂O (D_Cl ^ol/melt = 2.2?±?1.1 × 10^?4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65–78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F–Cl–Br–I–H₂O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280?°C and 0.3 GPa with (R ²?=?0.99): \(D_{F}^{\text{ol/melt}}\ =\ 3.6\pm 0.4\ \times \ {{10}^{-3}}\ \times \ {{X}_{{{\text{H}}_{\text{2}}}\text{O}}}\left( \text{wt }\!\!\%\!\!\text{ } \right)\ +\ 6\ \pm \ 0.4\times \,{{10}^{-4}}\). The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287–295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65–78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth’s mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.     

Temperature dependence of intersite distribution of Mg and Fe in olivine and the associated change of lattice parameters

The cation distribution of natural and heated ferromagnesian olivine with chemical composition, Fo₆₇Fa₃₃, from metagabbro was examined by X-ray diffraction. Heating and quenching experiments were made by a newly devised apparatus which enables us to obtain very fast quenching speed in comparison with the usual technique. The distribution constants, K _D=(Fe⁺²/Mg) _M1/(Fe⁺²/Mg) _M2, of the natural samples were less than 1.07, and those of heat-treated samples were more than 1.15, indicating that cation ordering takes place with temperature. The distribution of Fe⁺² and Mg is nearly random at low temperatures, whereas Fe⁺² shows a slight but significant preference for a smaller M1 site at high temperatures. The change of the distribution constant was observed on specimens which were heated for a short period of time (6–1,060 s) and quenched within 10 ms. Thus the rate of the cation reordering reaction is a very fast process. The lattice parameters b and c decrease whereas a increases with the increase of distribution constant. The overall effect on unit cell volume is a decrease with the increasing distribution constant, suggesting the presence of significant pressure dependence of the cation distribution towards the ordering of Fe at M1 site in ferromagnesian olivine.