The oxidation state of subcontinental mantle: oxygen thermobarometry of mantle xenoliths from central Asia

The oxygen fugacities of 48 mantle xenoliths from 5 localities in southern Siberia (USSR) and Mongolia have been determined. Ferric iron contents of spinels were measured by ⁵⁷Fe Mössbauer spectroscopy and oxygen fugacities calculated from spinel-olivineorthopyroxene equilibrium. The samples studied represent the major types of upper mantle lithologies including spinel and garnet peridotites and pyroxenites, fertile and depleted peridotites and anhydrous and metasomatized samples which come from diverse tectonic settings. Extensive geochemical and isotope data are also available for these samples. Oxygen fugacity values for most central Asian xenoliths fall within the range observed in peridotite xenoliths from other continental regions at or slightly below the FMQ buffer. However, xenoliths from the Baikal rift zone are the most reduced among xenoliths for which Mössbauer data on spinels are available. They yield fO₂ values similar to those in oceanic peridotites and MORBs, while xenoliths in other occurrences have higher fO₂s. In general, the continental lithosperic mantle is more oxidized than MORB-like oceanic mantle. This difference seems to be due to incorporation of oxidized material into some parts of the subcontinental mantle as a result of subduction of oceanic crust. Garnet- and garnet-spinel lherzolites from the Baikal rift area have slightly higher oxygen fugacities than shallower spinel lherzolites. Oxygen fugacity does not appear to be correlated with the degree of depletion of peridotites, and its values in peridotites and pyroxenites are very much alike, suggesting that partial melting (at least at moderate degrees) takes place at essentially the same fO₂s that are now recorded by the residual material. Modally (amphibole- and phlogopitebearing) and cryptically metasomatized xenoliths from the Baikal rift zone give the same fO₂ values as depleted anhydrous peridotites, suggesting that solid-melt-fluid reactions in the continental rift mantle also take place without substantial change in redox state. This is in contrast to other tectonic environments where metasomatism appears to be associated with oxidation.     

Redox state of the upper mantle

The oxygen fugacity condition of equilibration has been carefully determined from a spinel lherzolite from Mongolia, olivine xenocrysts from chrome pyrope-bearing peridotite nodules from kimberlites of Yakutia, and basaltic samples from ocean floor, iron arcs and the continental areas. These indicate that the spinel lherzolites occurring within alkali basalts from Mongolia, equilibrated under an \(f_{O_2 } \) condition similar to that of WM buffer. The diamond and chrome pyrope-bearing peridotites from the kimberlite pipes equilibrated between IW and WM buffers. Some of the ilmenite-bearing peridotite crystallized under \(f_{O_2 } \) conditions similar to that between WM and QFM buffers and chondrites equilibrated below the QFI buffer. It is concluded that during geochemical processes in the upper mantle the \(f_{O_2 } \) conditions vary broadly, and are similar to that between FMQ and IW buffers. There is a dramatic change in the composition of the kimberlitic fluid, which is CH₄-bearing at an early stage, but is in equilibrium with H₂O and CO₂ at a later stage. This is related to mass transfer of fluids from the lower part of the mantle with a low oxidation state to the upper part having a higher \(f_{O_2 } \) condition.     

Oxygen fugacity and geochemical variations in the martian basalts: implications for martian basalt petrogenesis and the oxidation state of the upper mantle of Mars

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.     

Metasomatic oxidation of upper mantle periodotite

Examination of Fe³⁺ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe³⁺ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (Fe_T) as Fe³⁺ (Fe³⁺/Fe_T=0.33); orthopyroxenes contain 0.06–0.09 Fe³⁺/Fe_T; spinels contain 0.30–0.40 Fe³⁺/Fe_T; olivines contain 0.01–0.06 Fe³⁺/Fe_T; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe³⁺/Fe_T. In each mineral, Fe³⁺ and Fe²⁺ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe³⁺/Fe_T ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe³⁺/Fe_T ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe³⁺/Fe_T ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe³⁺ into existing mineral grains rather than by oxidation of existing Fe²⁺ in peridotite mineral grains. The very high Fe³⁺/Fe_T ratio in the metasomatic amphibole may be a function of the high Fe³⁺/Fe_T of the metasomatic fluid, crystal chemical limitations on the amount of Fe³⁺ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe₂O₃. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe²⁺ and Fe³⁺ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe³⁺. With increasing distance from the dike, the ratio of added Fe³⁺ to added Fe²⁺ increases. The high Fe³⁺/Fe_T of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe³⁺/added Fe²⁺ in pyroxenes and spinel suggest that the Fe³⁺/Fe_T ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe³⁺ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe³⁺/Fe_T.     

CO2-CO fluid inclusions in a composite peridotite xenolith: implications for upper mantle oxygen fugacity

Fluid inclusions occur in a composite xenolith from the Lunar Crater Volcanic Field, Nevada, U.S.A. The xenolith is an amphibole-bearing wehrlite that is cut by an andesine-amphibole vein. The compositions of individual fluid inclusions in both portions of the xenolith have been determined using microthermometry and micro Laser-Raman spectroscopy. Fluids in the host wehrlite are nearly pure CO₂ (>99 mol%) whereas those in the vein contain from 8.5 to 12.0 mol % CO in CO₂. Chemical modelling shows that the composition of the vein fluids at T _room is representative of the composition at the high P, T conditions of trapping. Graphite has not been observed by optical microscopy in any of the fluid inclusions. Graphite is probably absent (although stable at T<800° C) most probably because of the kinetically unfavorable CO decomposition reaction and rapid quenching. By combining the measured fluid compositions with fluid P-V-T data and the chemical equilibrium CO₂CO +1/2 O₂, we have calculated the oxygen fugacity of the fluid inclusions at 1200° C: log 8.6 (vein) and –6 (host). If the of the fluid in the vein represents that in equilibrium with the magma that crystallized to produce the vein, then the of the basalt magma is near QFM at 1200° C and 10.3 kbar. This is similar to values reported for extrusive basaltic lavas. If the much lower intrinsic oxygen fugacity-values for divines and spinels from alkali basalt nodules are representative of upper mantle conditions, then oxidation of basaltic magmas must occur in the upper mantle prior to ascent to the surface. Implications for the origin of CO₂-rich fluids and carbon isotope geochemistry are also discussed.     

Single-crystal elastic properties of chondrodite: implications for water in the upper mantle

Chondrodite, a member of the humite group of minerals, forms by hydration of olivine and is stable over a range of temperatures and pressures that includes a portion of the uppermost mantle. We have measured the single crystal elastic properties of a natural chondrodite specimen at ambient conditions using Brillouin spectroscopy. The isotropic aggregate bulk (K) and shear (μ) moduli calculated from the single-crystal elastic moduli, C_ij, are: K_S=118.4(16) GPa and μ=75.6(7) GPa. A comparison of the structures and elasticity of olivine and chondrodite indicate that the replacement of O with (OH,F) in M²⁺O₆ octahedra has a small effect on the elasticity of humite-group minerals. The slightly diminished elastic moduli of humite-group minerals (as compared to olivine) are likely caused by a smaller ratio of strong structural elements (SiO₄ tetrahedra) to weaker octahedra, and perhaps a more flexible geometry of edge-sharing MO₄(O,OH,F)₂ octahedra. In contrast to the humite-olivine group minerals, the incorporation of water into garnets and spineloids leads to a more substantial decrease in the elastic properties of these minerals. This contrasting behavior is due to formation of O₄H₄ tetrahedra and vacant hydroxyl-bearing octahedra in the garnets and spineloids, respectively. Therefore, the mechanism of incorporation of H/OH into mineral phases, not only degree of hydration, should be taken into account when estimating the effect of water on the elastic properties of minerals. The bulk elastic wave velocities of chondrodite and olivine are very similar. If humite-like incorporation of OH is predominant in the upper mantle, then the reaction of OH with olivine will have a minor or possibly no detectable effect on seismic velocities. Thus, it may be difficult to distinguish chondrodite-bearing rocks from “anhydrous” mantle on the basis of seismically determined velocities for the Earth. Received: 25 February 1998 / Revised, accepted: 18 August 1998     

The state of the upper mantle beneath southern Africa

We present a new upper mantle seismic model for southern Africa based on the fitting of a large (3622 waveforms) multi-mode surface wave data set with propagation paths significantly shorter (≤ 6000 km) than those in globally-derived surface wave models. The seismic lithosphere beneath the cratonic region of southern Africa in this model is about 175 ± 25 km thick, consistent with other recent surface wave models, but significantly thinner than indicated by teleseismic body-wave tomography. We determine the in situ geotherm from kimberlite nodules from beneath the same region and find the thermal lithosphere model that best fits the nodule data has a mechanical boundary layer thickness of 186 km and a thermal lithosphere thickness of 204 km, in very good agreement with the seismic measurement. The shear wave velocity determined from analyzes of the kimberlite nodule compositions agree with the seismic shear wave velocity to a depth of 150 km. However, the shear wave velocity decrease at the base of the lid seen in the seismic model does not correspond to a change in mineralogy. Recent experimental studies of the shear wave velocity in olivine as a function of temperature and period of oscillation demonstrate that this wave speed decrease can result from grain boundary relaxation at high temperatures at the period of seismic waves. This decrease in velocity occurs where the mantle temperature is close to the melting temperature (within 100 °C).     

Storage of F and Cl in the upper mantle: geochemical implications

Electron microprobe analyses yielded mean values of $\text{F}\text{0.43}\text{and}\text{Cl}\text{0.08}\text{wt.}\text{\%}$ for primary-textured phlogopites in coarse, depleted garnet-lherzolite xenoliths from kimberlites. Most secondary-textured phlogopites have too low Cl (0.01–0.08 wt.%) to be metamorphic precursors of primary-textured phlogopites. MARID-suite phlogopites and many megacrysts in kimberlites have low Cl ($\text{～ 0.02}\text{wt.}\text{\%}$), and some but not necessarily all secondary micas may result from infiltration of kimberlite into peridotite xenoliths. A good correlation between P and F in some oceanic basalts and gabbros might suggest that these elements are derived mainly from F-rich apatite inthe mantle, and that whitlockite is not present in the source region. Mantle-derived mica and amphibole have such low Cl that it is necessary to attribute Cl in oceanic basalts and gabbros either to substantial Cl in the source apatite, or to Cl from invading solutions, or both: three apatites from the mantle contain 0.8–1.0 wt.% Cl, and others contain lower amounts. The halogen contents of kimberlitic magmas can be explained by incorporation of Cl-bearing mica and F-rich apatite during melting of peridotites, but compositional constraints are weak.     

A note on the calibration of the garnet-cordierite geothermometer and geobarometer

Experimental and theoretical considerations indicate that the distribution coefficient for iron and magnesium between coexisting garnet and cordierite increases with temperature in the assemblage cordierite-garnet-sillimanite-quartz. This conclusion is confirmed by distribution coefficients from natural garnet and cordierite from geologically well defined settings. The only published calibration which incorporates this feature is that of Currie (1971), and this is the only calibration which can be qualitatively correct although it may be wrong in detail. Other calibrations encounter catastrophes, particularly in andalusite-bearing assemblages.     

The trapped fluid phase in upper mantle xenoliths from Victoria,Australia: implications for mantle metasomatism

Mantle-derived xenoliths of spinel lherzolite, spinel pyroxenite, garnet pyroxenite and wehrlite from Bullenmerri and Gnotuk maars, southwestern Victoria, Australia contain up to 3 vol.% of fluids trapped at high pressures. The fluid-filled cavities range in size from fluid inclusions (1–100 m) up to vugs 11/2 cm across, lined with euhedral high-pressure phases. The larger cavities form an integral part of the mosaic microstructure. Microthermometry and Raman laser microprobe analysis show that the fluids are dominantly CO₂. Small isolated inclusions may have densities 1.19 g/cm³, but most inclusions show microstructural evidence of partial decrepitation during eruption, and these have lower fluid densities. Mass-spectrometric analysis of gases released by crushing or heating shows the presence of He, N₂, Ar, H₂S, CO_s and SO₂ in small quantities; these may explain the small freezing-point depressions observed in some inclusions. Petrographic, SEM and microprobe studies show that the trapped fluids have reacted with the cavity walls (in clinopyroxene grains) to produce secondary amphiboles and carbonates. The trapped CO₂ thus represents only a small residual proportion of an original volatile phase, which has undergone at least two stages of modification — first by equilibration with spinel lherzolite to form amphibole (±mica±apatite), then by limited reaction with the walls of the fluid inclusions. The inferred original fluid was a CO₂-H₂O mixture, with significant contents of (at least) Cl and sulfur species. Generation of this fluid phase in the garnet-peridotite stability field, followed by its migration to the spinel peridotite stability field, would provide an efficient mechanism for metasomatic enrichment of the upper mantle in LIL elements. This migration could involve either a volatile flux or transport in small volumes of silicate melt that crystallize in the spinel peridotite field. These observations suggest that some portions of the subcontinental upper mantle contain large reservoirs of free fluid CO₂, which may be liberated during episodes of rifting or magmatism, to induce granulite-facies metamorphism of the lower crust.     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.     

Garnet inclusions in diamond and the state of the upper mantle

Temperature and pressure estimates for Earth's upper mantle generally are based on indirect information derived from phase equilibria studies and the measurement of temperature and pressure dependent physical and chemical properties for relevant mantle materials. This paper describes an alternative approach, based on solid-inclusion piezothermometry, which utilizes the thermoelastic properties of direct mantle derived mineral samples. In particular, this study provides the theoretical development, based on the Murnaghan equation of state for solids, for a simple method of calculating isomeke lines for host and inclusion minerals of cubic symmetry which may be extrapolated accurately to upper mantle pressure and temperature conditions. The method is demonstrated for the particular case of garnet inclusions in diamond, for which adequate laboratory thermoelastic data are available. A specific application is made in the evaluation of the depth of formation of the D1 garnet-diamond inclusion system described by Harris et al. (1970). The pressure and temperature conditions of inclusion formation lie along the calculated isomeke line within the range constrained by recent graphite-diamond phase equilibria data. However, because the isomeke line for the garnet-diamond system and the graphite-diamond phase transition are very similar in slope, a further constraint is required. Assuming, therefore, that temperature in the upper mantle is bounded by the “Oceanic” and “Shield” geotherms of Clark and Ringwood (1964), the present results indicate that the D1 garnet-diamond system formed within the depth range 138 to 155 km (about 45 to 53 kbar pressure). This result, which relates to the genesis of kimberlite xenoliths, is generally consistent with the results of other studies which utilize phase equilibria data.     

Orthopyroxene-magnetite-quartz oxygen barometer for Mnbearing rocks (experimental calibration)

The compositions of orthopyroxene, associated with magnetite and quartz in the system FeO-MgO-MnO-SiO₂ were determined experimentally at temperatures of 700, 750, 800°C and pressures ranging between 3 and 5 kbar. On the basis of data obtained the value of the Guggenheim parameter of orthopyroxene solid solution was calculated: A_{Fe. Mn} = 2400 ±500 cal. For rocks rich in MnO, a modified version of orthopyroxene-magnetite-quartz oxygen barometer is suggested.     

Regression diagnostics and robust regression in geothermometer/geobarometer calibration: the garnet-clinopyroxene geothermometer revisited

Abstract The calibration of geothermometers and geobarometers should involve not only the determination of the parameters in the equation used, but also the uncertainties on, and the correlations between, these parameters. This necessitates the use of a technique such as least squares. Given the poor performance of least squares in the presence of outliers in the data, techniques for identifying outliers for exclusion—regression diagnostics, and techniques for handling data which include outliers—robust regression and jackknifing, are essential. These techniques are summarized and their importance is emphasized, and they are applied to the calibration of the garnet-clinopyroxene Fe-Mg exchange geothermometer.
The experimental data of Raheim & Green (1974) and Ellis & Green (1979) are explored using regression diagnostics to discover outliers in the data. After exclusion of the two influential outliers found, a new geothermometer equation for garnet-clinopyroxene Fe-Mg exchange is derived using robust regression and based on all the data: thus, T (K) = 2790 + 10 P + 3140x_ca,g/1.735 + In K _D where T is in Kelvin and P is in kbar. This equation, as might be hoped, is essentially identical to that of Ellis & Green (1979). Equations for calculating the uncertainty in a calculated temperature, contributed by uncertainties in the calibration, are also derived.     

Experimental phase and melting relations of metapelite in the upper mantle: implications for the petrogenesis of intraplate magmas

We performed a series of piston-cylinder experiments on a synthetic pelite starting material over a pressure and temperature range of 3.0–5.0 GPa and 1,100–1,600°C, respectively, to examine the melting behaviour and phase relations of sedimentary rocks at upper mantle conditions. The anhydrous pelite solidus is between 1,150 and 1,200°C at 3.0 GPa and close to 1,250°C at 5.0 GPa, whereas the liquidus is likely to be at 1,600°C or higher at all investigated pressures, giving a large melting interval of over 400°C. The subsolidus paragenesis consists of quartz/coesite, feldspar, garnet, kyanite, rutile, ±clinopyroxene ±apatite. Feldspar, rutile and apatite are rapidly melted out above the solidus, whereas garnet and kyanite are stable to high melt fractions (>70%). Clinopyroxene stability increases with increasing pressure, and quartz/coesite is the sole liquidus phase at all pressures. Feldspars are relatively Na-rich [K/(K + Na) = 0.4–0.5] at 3.0 GPa, but are nearly pure K-feldspar at 5.0 GPa. Clinopyroxenes are jadeite and Ca-eskolaite rich, with jadeite contents increasing with pressure. All supersolidus experiments produced alkaline dacitic melts with relatively constant SiO₂ and Al₂O₃ contents. At 3.0 GPa, initial melting is controlled almost exclusively by feldspar and quartz, giving melts with K₂O/Na₂O ~1. At 4.0 and 5.0 GPa, low-fraction melting is controlled by jadeite-rich clinopyroxene and K-rich feldspar, which leads to compatible behaviour of Na and melts with K₂O/Na₂O ≫ 1. Our results indicate that sedimentary protoliths entrained in upwelling heterogeneous mantle domains may undergo melting at greater depths than mafic lithologies to produce ultrapotassic dacitic melts. Such melts are expected to react with and metasomatise the surrounding peridotite, which may subsequently undergo melting at shallower levels to produce compositionally distinct magma types. This scenario may account for many of the distinctive geochemical characteristics of EM-type ocean island magma suites. Moreover, unmelted or partially melted sedimentary rocks in the mantle may contribute to some seismic discontinuities that have been observed beneath intraplate and island-arc volcanic regions.     

High pressure fluids in the system MgO–SiO2–H2O under upper mantle conditions

Fluids and melts have been trapped and analysed in high pressure experiments in the model mantle system MgO-SiO₂-H₂O at 6 to 10.5 GPa and 900 to 1,200 °C. The fluid/melt traps consisted of a diamond layer that was added to the experimental charge and was separate from the silicate phases. The recovered diamond traps were analysed by laser ablation - ICP - MS. Starting materials were synthetic mixtures of brucite, talc and silica with variable Mg/Si containing 11-31 wt% H₂O. Experiments on a serpentine starting composition [Mg₃Si₂O₅(OH)₄] result in MgO/SiO₂ weight ratios in the subsolidus fluids close to 1 at 6 GPa and close to 2 at 9 GPa. Melt compositions at 6 and 9 GPa have MgO/SiO₂ ratios close to that of forsterite. At a single pressure the amount of dissolved silicate in the fluid increases steadily with increasing temperature up to 1,150 °C, where a sudden increase of both SiO₂ and MgO is observed. This discrete step marks the solidus, which is more clearly developed at 6 than at 9 GPa. Thus, hydrous melts within the model mantle subsystem Mg₂SiO₄-Mg₂Si₂O₆-H₂O are chemically distinct from aqueous fluids up to at least 9 GPa, corresponding to 300 km depth. Extrapolation of the current data set implies that total convergence between fluid and melt along the solidus probably occurs at 12-13 GPa (~400 km), i.e. close to the Earth's mantle transition zone. Beneath cratons, interactions of hydrous fluids with upper mantle lithologies cause relative silica depletion (olivine enrichment) at depths greater than 200 km and silica (orthopyroxene) enrichment at shallower depths.     

Empirical calibration of the silica–Ca-tschermak's–anorthite (SCAn) geobarometer

The pressure-sensitive equilibrium among anorthite, quartz and the Ca-tschermak component in clinopyroxene (CaAl₂SiO₆; CaTs), CaAl₂SiOCpx6+SiOQtz2=CaAl₂Si₂OPl8 (SCAn) ,can be used as a geobarometer in granulites with the proper assemblage, and has been calibrated using mineral composition data from partial melting experiments of natural assemblages and from phase equilibrium experiments on the end-member CMAS system. The experimental data cover the P – T  range 4–32  kbar and 900–1400  °C. Linear least-squares regression analysis of the experimental data resulted in the following empirical expressions for pressure in terms of composition and temperature: P = 5.066 [±0.760]+ 1300 [±800] T  −ln K 276 [±16] · T  [±2.5  kbar]or P = 6.330 [±0.116]−ln K 301 [±9]· T  [±1.0  kbar] ,where K = a PlAn a CpxCaTs  .The first equation incorporates an enthalpy term, but is less accurate than the second equation, in which the enthalpy of reaction is ignored. Application of these expressions to natural and experimental equilibrium mineral assemblages demonstrates that the empirical barometers are applicable over a wide range of pressures (≥4  kbar), temperatures (≥700  °C) and bulk compositions (Mg#≥32.5).     

Oxidation state of lithospheric mantle along the northeastern margin of the North China Craton: implications for geodynamic processes

Quaternary volcanic rocks in the Kuandian (KD), Longgang (LG), Changbaishan (CBS), Wangqing (WQ), and Jilin (JL) volcanic centres in eastern Liaoning and southern Jilin provinces contain mantle xenoliths of spinel-facies lherzolites and minor harzburgites. Among the study sites, the KD, LG, and CBS volcanic fields are located on the northeastern margin of the North China Craton (NCC), whereas the WQ and JL fields lie on the southern margin of the Xing'an–Mongolia Orogenic Belt (XMOB). The (Fo) components of olivine (Ol) and Cr# (=Cr/(Cr + Al)) of spinel, together with trace element abundance of clinopyroxene, suggest that the subcontinental lithospheric mantle (SCLM) in the study area has undergone a low degree (4–6%) of partial melting. The rocks do not show modal metasomatism, but clinopyroxene grains in selected samples show elevated large ion lithophile element compositions, suggesting that the mantle xenoliths underwent minor cryptic metasomatism by exchange with a silicate melt. Two-pyroxene thermometry yielded equilibration temperatures ranging from 740°C to 1210°C. The corresponding oxygen fugacity (fO₂) was calculated to range from FMQ –2.64 to +0.39 with an average of –0.59 (n?=?53). The oxidation state is comparable to that of abyssal peridotites and the asthenospheric mantle. We failed to discover differences in equilibration temperatures and oxidation state between lherzolites and harzburgites, suggesting that partial melting did not affect fO₂ values. In addition, similar fO₂ of non-metasomatized and metasomatized samples suggest that metasomatism in the region did not affect fO₂. Our data suggest that the present SCLM beneath the northeastern margin of the NCC and the southern margin of the XMOB are very similar and likely formed from a fertile asthenosphere after delamination of an old lithospheric keel below the NCC in response to the west-dipping subduction of the Pacific oceanic plate since early to middle Mesozoic time.     

Intrinsic oxygen fugacity measurements: techniques and results for spinels from upper mantle peridotites and megacryst assemblages

A new technique for the determination of intrinsic oxygen fugacities () of single and polyphase geological samples with solid ZrO₂, oxygen-specific electrolytes is described. Essentially the procedure involves isolating the emf signal from the sample from that unavoidably imposed by the residual atmosphere inside the sample-bearing sensor. By varying the of the residual atmosphere, it is possible to determine a ‘plateau’ value of constant recorded from the sensor which represents a reversed intrinsic measurement for the sample alone, and where the extent of the plateau reflects the innate buffering capability of the sample. A measure of the precision and accuracy of the data obtained is the fact that identical values are obtained whether on a heating or cooling cycle of the sample + compatible atmosphere system.These techniques have been applied to measurements of the intrinsic of spinels from peridotites and megacryst assemblages from Australia, West Germany and the U.S.A. Oxidation states range from ～- 0.25 log₁₀ units more oxidized to 1 log₁₀ unit more reduced than the iron-wüstite (IW) buffer. The overall reduced nature of the spinels and the range of 's obtained are striking features of the data. One implication of the results is that the majority of mantle-derived magmas are initially highly reduced, and the relatively oxidized values observed at surface (～- 4–5 log₁₀ orders more oxidized than IW) reflect late-stage alteration, perhaps by H₂ loss (Sato, 1978).