Calculated Oxygen Fugacities Research Articles

Decoding magma plumbing and geochemical evolution beneath the Lastarria volcanic complex (Northern Chile)—Evidence for multiple magma storage regions

The petrology of quaternary andesites and dacites from Lastarria volcano was investigated to reconstruct the magma plumbing and storage conditions beneath the volcano. The mineral phase compositions and whole-rock major and trace element compositions were used to constrain temperature, pressure and possible mechanisms for magma differentiation. The applied thermobarometric models include two-pyroxene thermobarometry, plagioclase-melt thermometry, amphibole composition thermobarometry, and Fe-Ti oxide thermo-oxybarometry. The overall temperature estimation is in the range 840°C to 1060°C. Calculated oxygen fugacity ranges between NNO to NNO+1. Results of the geo-barometric calculations reveal multiple magma storage regions, with a distinct storage level in the uppermost crust (~6.5–8km depth), a broad zone at mid-crustal levels (~10–18km depth), and a likely deeper zone at intermediate to lower crustal levels (>20km depth). The highest temperatures in the range 940–1040°C are recorded in minerals stored in the mid-crustal levels (~10–18km depth). The whole-rock compositions clearly indicate that magma mixing is the main parameter controlling the general differentiation trends. Complex zoning patterns and textures in the plagioclase phenocrysts confirm reheating and remobilization processes due to magma replenishment.

Redox variations in the inner solar system with new constraints from vanadium XANES in spinels

![][1] Many igneous rocks contain mineral assemblages that are not appropriate for application of common mineral equilibria or oxybarometers to estimate oxygen fugacity. Spinel-structured oxides, common minerals in many igneous rocks, typically contain sufficient V for XANES measurements, allowing use of the correlation between oxygen fugacity and V K pre-edge peak intensity. Here we report V pre-edge peak intensities for a wide range of spinels from source rocks ranging from terrestrial basalt to achondrites to oxidized chondrites. The XANES measurements are used to calculate oxygen fugacity from experimentally produced spinels of known ![Formula][2] . We obtain values, in order of increasing ![Formula][3] , from IW-3 for lodranites and acapulcoites, to diogenites, brachinites (near IW), ALH 84001, terrestrial basalt, hornblende-bearing R chondrite LAP 04840 (IW+1.6), and finally ranging up to IW+3.1 for CK chondrites (where the ![Formula][4] of a sample relative to the ![Formula][5] of the IW buffer at specific T ). To place the significance of these new measurements into context we then review the range of oxygen fugacities recorded in major achondrite groups, chondritic and primitive materials, and planetary materials. This range extends from IW-8 to IW+2. Several chondrite groups associated with aqueous alteration exhibit values that are slightly higher than this range, suggesting that water and oxidation may be linked. The range in planetary materials is even wider than that defined by meteorite groups. Earth and Mars exhibit values higher than IW+2, due to a critical role played by pressure. Pressure allows dissolution of volatiles into magmas, which can later cause oxidation or reduction during fractionation, cooling, and degassing. Fluid mobility, either in the sub-arc mantle and crust, or in regions of metasomatism, can generate values >IW+2, again suggesting an important link between water and oxidation. At the very least, Earth exhibits a higher range of oxidation than other planets and astromaterials due to the presence of an O-rich atmosphere, liquid water, and hydrated interior. New analytical techniques and sample suites will revolutionize our understanding of oxygen fugacity variation in the inner solar system, and the origin of our solar system in general. [1]: /embed/graphic-1.gif [2]: /embed/mml-math-1.gif [3]: /embed/mml-math-2.gif [4]: /embed/mml-math-3.gif [5]: /embed/mml-math-4.gif

Iron isotope systematics in planetary reservoirs

Iron is the only polyvalent major element, and controls reduction–oxidation (redox) reactions in a host of geologic processes and reservoirs, from the mineral- to planetary-scale, on Earth and in space. Mass transfer of Fe is often accompanied by changes in bonding environment, meaning the resultant variation in bond-strength in crystals, liquids and gases induces stable isotope fractionation, even at high temperatures. In the absence of iron exchange, electron transfer can also affect iron's valence state and calculated oxygen fugacity (fO2), however its isotope composition remains unchanged. Thus, iron isotopes are a powerful tool to investigate processes that involve mass transfer, redox reactions and changes in bonding environment in planetary systems. Primitive chondritic meteorites show remarkable isotopic homogeneity, δ57Fe=−0.01±0.01‰ (2SE), over a wide range of Fe/Mg vs Ni/Mg, a proxy for fO2 in the solar nebula. In chondrites, there are iron isotope differences between metal and silicates that become more pronounced at higher metamorphic grades. However, on a planetary scale, Mars and Vesta overlap with chondrites, preserving no trace of core formation or volatile depletion on these bodies. Upon assessment of pristine lherzolites, the Bulk Silicate Earth is heavier than chondrites (δ57Fe=+0.05±0.01‰; 2SE), and similar to or slightly lighter than the Moon. That the mantles of some differentiated inner solar system bodies extend to heavier compositions (+0.2‰) than chondrites may principally result from volatile depletion either at a nebular or late accretion stage. Within terrestrial silicate reservoirs, iron isotopes provide insight into petrogenetic and geodynamic processes. Partial melting of the upper mantle produces basalts that are heavier than their sources, scaling with degree of melting and driving the increasingly refractory peridotite to lighter compositions. Mid-Ocean Ridge Basalts (MORBs) are homogeneous to δ57Fe=0.10±0.01‰ (2SE) after correction to primary magmas, and can be produced from single stage melt extraction. Conversely, iron isotopes in arc basalts are more varied (−0.2<δ57Fe(‰)<+0.2) than can be produced from partial melting. Their iron isotope compositions are significantly lighter, suggesting they form from mantle re-enriched in light Fe and/or more depleted than Depleted MORB Mantle (DMM). If arc sources are more oxidised, an agent other than iron is required. Magmatic differentiation drives enrichment in heavy isotopes by partial melting of crustal rocks, fluid exsolution and crystallisation. Iron isotope trajectories in evolving magmas depend on their initial fO2 and whether the system is closed or open to oxygen and/or mass exchange. Granite end-members carry signatures diagnostic of their tectonic setting, where reduced, anorogenic A-type granites (δ57Fe=+0.4‰) are heavier than more oxidised I-types (δ57Fe=+0.2‰).

Hydrothermal alteration of seafloor peridotites does not influence oxygen fugacity recorded by spinel oxybarometry

Abstract Olivine, orthopyroxene, and spinel compositions within seafloor peridotites yield important information about the nature of Earth’s mantle. Major element compositions of these minerals can be used to calculate oxygen fugacity, a thermodynamic property critical to understanding phase equilibria in the upper mantle. This study examines how hydrothermal alteration at the seafloor influences peridotite chemistry. The Tonga Trench (South Pacific Ocean) exposes lithospheric forearc peridotites that range from highly altered to completely unaltered and provides an ideal sample suite for investigating the effect of alteration on spinel peridotite major element chemistry and calculated oxygen fugacity. Using the Tonga peridotites, we develop a qualitative alteration scale rooted in traditional point-counting methodology. We show that high degrees of serpentinization do not affect mineral parameters such as forsterite number in olivine, iron site occupancy in orthopyroxene, and Fe3+/ΣFe ratio in spinel. Additionally, while serpentinization is a redox reaction that leaves behind an oxidized residue, the oxygen fugacity recorded by mantle minerals is unaffected by nearby low-temperature serpentinization. As a result, oxygen fugacity measured by spinel oxybarometry in seafloor peridotites is representative of mantle processes, rather than an artifact of late-stage seafloor alteration.

Garnet and Spinel Oxybarometers: New Internally Consistent Multi-equilibria Models with Applications to the Oxidation State of the Lithospheric Mantle

New thermodynamic data for skiagite garnet (Fe3Fe23+Si3O12) are derived from experimental phase-equilibrium data that extend to 10 GPa and are applied to oxybarometry of mantle peridotites using a revised six-component garnet mixing model. Skiagite is more stable by 12 kJ mol–1 than in a previous calibration of the equilibrium 2 skiagite = 4 fayalite + ferrosilite + O2, and this leads to calculated oxygen fugacities that are higher (more oxidized) by around 1–1·5 logfO2log⁡fO2 units. A new calculation method and computer program incorporates four independent oxybarometers (including 2 pyrope + 2 andradite + 2 ferrosilite = 2 grossular + 4 fayalite + 3 enstatite + O2) for use on natural peridotite samples to yield optimum logfO2log⁡fO2 estimates by the method of least squares. These estimates should be more robust than those based on any single barometer and allow assessment of possible disequilibrium in assemblages. A new set of independent oxybarometers for spinel-bearing peridotites is also presented here, including a new reaction 2 magnetite + 3 enstatite = 3 fayalite + 3 forsterite + O2. These recalibrations combined with internally consistent PT determinations for published analyses of mantle peridotites with analysed Fe2O3 data for garnets, from both cratonic (Kaapvaal, Siberia and Slave) and circumcratonic (Baikal Rift) regions, provide revised estimates of oxidation state in the lithospheric mantle. Estimates of logfO2log⁡fO2 for spinel assemblages are more reduced than those based on earlier calibrations, whereas garnet-bearing assemblages are more oxidized. Importantly, this lessens considerably the difference between garnet and spinel oxybarometry that was observed with previous published calibrations.

Natural moissanite (SiC) – a low temperature mineral formed from highly fractionated ultra-reducing COH-fluids

Natural moissanite (SiC) is reported from dozens of localities, most commonly from ultramafic rocks where it may be associated with diamond and iron silicides. Yet, formation conditions of moissanite remain in the realm of speculation. The key property of SiC is its extremely reduced nature. We have experimentally equilibrated SiC with olivine and orthopyroxene at 1300-1700°C, 2 and 10 GPa, to determine the oxygen fugacity of the C + orthopyroxene = SiC + olivine + O2 buffer (MOOC) and the equilibrium XMg of coexisting mantle silicates. The experiments resulted in olivine and orthopyroxene with XMg of 0.993-0.998 in equilibrium with SiC and iron silicides. Calculated oxygen fugacities are 5-6.5 log units below the iron-wustite (IW) buffer at 2-10 GPa. The experimental results concur with calculated phase relations for harzburgitic mantle under reducing conditions that include metal alloys, carbides and silicides. The extremely reducing character of SiC precludes coexistence with silicates with appreciable Fe 2+ , and hence excludes equilibrium with mantle phases with typical XMg’s of ~0.9. Calculated Fe-Mg diffusion lengths reveal that SiC grains of 1 mm would react with the Fe-component of olivine to iron carbide or metal and orthopyroxene within <1 Ma at te mperatures above 800°C. We thus conclude that SiC forms through a low-temperature process (<700-800°C) where equilibrium is only reached at the grain scale. The most plausible formation mechanism is a strong fractionation of a C-O-H fluid from metamorphosed sediments originally rich in organic material. Such a fluid is initially saturated with graphite or diamond and is slightly more reduced than the H2O-C join. Fluid percolation in the mantle leads to H2O-sequestration by crystallizing hydrous phases (most likely serpentine, brucite or phase A), and hence O2-removal from the fluid causing its reduction and continuous graphite or diamond precipitation. A small, highly fractionated fluid fraction may then reach CH4 and H2 concentrations that allow SiC formation on grain boundaries without equilibration with the bulk rock on a larger scale. Such a mechanism is corroborated by the strongly negative δ 13 C of moissanites (-20 to -37), consistent with reduced fluids originating from

Variations in Fe3+/∑Fe of Mariana Arc Basalts and Mantle Wedge fO2

Arc basalts are more oxidized than mid-ocean ridge basalts, but it is unclear whether this difference is due to differentiation processes in the Earth’s crust or to a fundamental difference in the oxygen fugacity of their mantle sources. Distinguishing between these two hypotheses is important for understanding redox-sensitive processes related to arc magmatism, and thus more broadly how Earth materials cycle globally. We present major, volatile, and trace element concentrations in combination with Fe^(3+)/∑Fe ratios determined in olivine-hosted glass inclusions and submarine glasses from five Mariana arc volcanoes and two regions of the Mariana Trough. For single eruptions, Fe^(3+)/∑Fe ratios vary along liquid lines of descent that are either slightly oxidizing (olivine + clinopyroxene + plagioclase fractionation, CO_2 ± H_2O degassing) or reducing (olivine + clinopyroxene + plagioclase ± magnetite fractionation, CO_2 + H_2O + S degassing). Mariana samples are consistent with a global relationship between calc-alkaline affinity and both magmatic H_2O and magmatic oxygen fugacity, where wetter, higher oxygen fugacity magmas display greater affinity for calc-alkaline differentiation. We find, however, that low-pressure differentiation cannot explain the majority of variations observed in Fe^(3+)/∑Fe ratios for Mariana arc basalts, requiring primary differences in magmatic oxygen fugacity. Calculated oxygen fugacities of primary mantle melts at the pressures and temperatures of melt segregation are significantly oxidized relative to mid-ocean ridge basalts (∼QFM, where QFM is quartz–fayalite–magnetite buffer), ranging from QFM + 1·0 to QFM + 1·6 for Mariana arc basalts, whereas back-arc related samples record primary oxygen fugacities that range from QFM + 0·1 to QFM + 0·5. This Mariana arc sample suite includes a diversity of subduction influences, from lesser influence of a homogeneous H_2O-rich component in the back-arc, to sediment melt- and fluid-dominated influences along the arc. Primary melt oxygen fugacity does not correlate significantly with sediment melt contributions (e.g. Th/La), nor can it be attributed to previous melt extraction in the back-arc. Primary melt oxygen fugacity correlates strongly with indices of slab fluids (e.g. Ba/La) from the Mariana Trough through the Mariana arc, increasing by 1·5 orders of magnitude as Ba/La increases by a factor of 10 relative to mid-ocean ridge basalts. These results suggest that contributions from the slab to the mantle wedge may be responsible for the elevated oxygen fugacity recorded by Mariana arc basalts and that slab fluids are potentially very oxidized.

Diversity in early crustal evolution: 4100 Ma zircons in the Cathaysia Block of southern China.

Zircons are crucial to understanding the first 500 Myr of crustal evolution of Earth. Very few zircons of this age (>4050 Ma) have been found other than from a ~300 km diameter domain of the Yilgarn Craton, Western Australia. Here we report SIMS U-Pb and O isotope ratios and trace element analyses for two ~4100 Ma detrital zircons from a Paleozoic quartzite at the Longquan area of the Cathaysia Block. One zircon (207Pb/206Pb age of 4127 ± 4 Ma) shows normal oscillatory zonation and constant oxygen isotope ratios (δ18O = 5.8 to 6.0‰). The other zircon grain has a ~4100 Ma magmatic core surrounded by a ~4070 Ma metamorphic mantle. The magmatic core has elevated δ18O (7.2 ± 0.2‰), high titanium concentration (53 ± 3.4 ppm) and a positive cerium anomaly, yielding anomalously high calculated oxygen fugacity (FMQ + 5) and a high crystallization temperature (910°C). These results are unique among Hadean zircons and suggest a granitoid source generated from dry remelting of partly oxidizing supracrustal sediments altered by surface waters. The ~4100 Ma dry melting and subsequent ~4070 Ma metamorphism provide new evidence for the diversity of the Earth's earliest crust.

Northwest Africa 4797: A strongly shocked ultramafic poikilitic shergottite related to compositionally intermediate Martian meteorites

Abstract– Northwest Africa (NWA) 4797 is an ultramafic Martian meteorite composed of olivine (40.3 vol%), pigeonite (22.2%), augite (11.9%), plagioclase (9.1%), vesicles (1.6%), and a shock vein (10.3%). Minor phases include chromite (3.4%), merrillite (0.8%), and magmatic inclusions (0.4%). Olivine and pyroxene compositions range from Fo66–72,En58–74Fs19–28Wo6–15, and En46–60Fs14–22Wo34–40, respectively. The rock is texturally similar to “lherzolitic” shergottites. The oxygen fugacity was QFM−2.9 near the liquidus, increasing to QFM−1.7 as crystallization proceeded. Shock effects in olivine and pyroxene include strong mosaicism, grain boundary melting, local recrystallization, and pervasive fracturing. Shock heating has completely melted and vesiculated igneous plagioclase, which upon cooling has quench‐crystallized plagioclase microlites in glass. A mm‐size shock melt vein transects the rock, containing phosphoran olivine (Fo69–79), pyroxene (En44–51Fs14–18Wo30–42), and chromite in a groundmass of alkali‐rich glass containing iron sulfide spheres. Trace element analysis reveals that (1) REE in plagioclase and the shock melt vein mimics the whole rock pattern; and (2) the reconstructed NWA 4797 whole rock is slightly enriched in LREE relative to other intermediate ultramafic shergottites, attributable to local mobilization of melt by shock. The shock melt vein represents bulk melting of NWA 4797 injected during pressure release. Calculated oxygen fugacity for NWA 4797 indicates that oxygen fugacity is decoupled from incompatible element concentrations. This is attributed to subsolidus re‐equilibration. We propose an alternative nomenclature for “lherzolitic” shergottites that removes genetic connotations. NWA 4797 is classified as an ultramafic poikilitic shergottite with intermediate trace element characteristics.

Chromite-hosted Silicate Melt Inclusions from Basalts in the Stravaj Complex, Southern Mirdita Ophiolite Belt (Albania)

The Stravaj ophiolite compex, part of the western Mirdita ophiolite belt in Albania, is located east of the Shpati massif, and west of the Shebenik massif. The Stravaj ophiolite sequence itself consist of MOR-related and subduction-related volcanic rocks (Hoeck et al. 2007) formed by pillow lavas and various dykes. The deeper units are formed by gabbros and plagioclase-bearing peridotites. The pillow lavas are intersected by basaltic dykes with a rather primitive composition. The studied basaltic dyke contains former relics of olivine, fresh spinel and clinopyroxene phenocrysts in a glassy groundmass. The silicate phases are strongly altered. The spinels appear as fresh, opaque grains preserved in totally altered olivine phenocrysts. The spinels host negative crystal shaped, multiphase silicate melt inclusions. The inclusions consist commonly of clinopyroxene daughter minerals, glass and rare sulphide blebs. A series of heating experiments were conducted, using the furnace technique to homogenize the silicate melt, in order to obtain homogenized silicate melt inclusions for major and trace element composition analysis and to determine their homogenization temperatures. Therefore, samples were heated to and quenched from 1200±20°C to 1240°C. The melt inclusions homogenized between 1220-1240±20°C. The major element composition of the homogenized melt inclusions is 48.3-51.2 wt% SiO2, 5.4-6.7 wt% FeO, 9.9-12.6 wt% MgO, 14.5-17.3 wt% Al2O3, 1.9-2.4 wt% Na2O and 12.1-13.0 wt% CaO. This result is highly comparable with the host mafic rock composition. The trace element composition of the homogenized silicate melt shows characteristic LREE-depleted patterns (La: 0.24-0.35 ppm), while the MREE and HREE patterns are generally flat: average PM-normalized La/Lu is 0.094. The average contents of compatible trace elements such as Cr, Ni, V, Co are up to 621 ppm, 825 ppm, 235 ppm and 80 ppm, respectively. Based on the major composition, trace element characteristics and the calculated oxygen fugacity, the studied silicate melt inclusions show strong similarities to MOR-related volcanic rocks found commonly in the Stravaj Massif. These chromite-bearing basalt dykes define extreme primitive MORB related melts in the upper part of the pillow lava section.

Composition of the mantle lithosphere beneath south-central Laurentia: Evidence from peridotite xenoliths, Knippa, Texas

Mantle xenoliths in ∼83 Ma basanites from south-central Texas provide a rare opportunity to examine the lithospheric mantle beneath southern Laurentia. These peridotites represent lithosphere at the boundary between Mesoproterozoic continental lithosphere and transitional Gulf of Mexico passive margin. Here we report petrographic, mineral, and major element data for 29 spinel peridotite xenoliths from Knippa and use these to characterize the lithospheric mantle beneath south central Texas. The xenoliths comprise spinel-bearing lherzolites and harzburgites with coarse, equigranular textures. Some peridotites contain veins of lizardite. There are no pyroxenites or eclogites. The peridotites contain olivine (Fo89-92), orthopyroxene (En89-92), clinopyroxene (Wo40-45En45-49Fs3-5), and spinel. Spinel Cr# (Cr/(Cr+Al)) distinguishes lherzolites (Cr# = 0.14–0.21) and harzburgites (Cr# = 0.25–0.36). Mineral and major element compositions indicate that the lherzolites are residues after <10% melt extraction from primitive upper mantle and the harzburgites formed by <15% melt extraction. Calculated oxygen fugacities indicate equilibration of the harzburgites at –1 to +0.61 and lherzolites at 0 to –2.6 log units with respect to fayalite-magnetite-quartz (FMQ) buffer, similar to lightly metasomatized spinel peridotites elsewhere. The degree of melt depletion and oxidation of the Knippa peridotites are consistent with present data sets for slightly metasomatized lithospheric mantle and/or backarc samples rather than forearc settings. Equilibration temperatures range from 824 to 1058 °C (mean= 916 °C), calculated at reference pressure of 2.0 GPa. Calculated mean seismic velocities Vs = 4.44 km/sec and Vp =7.87 km/sec show no systematic difference between lherzolites and harzburgites, and agree with present geophysical measurements of upper mantle velocity beneath Texas. The seismic velocities calculated for these samples will provide important constraints for interpretation of EarthScope and other geophysical data sets.

The petrology of high pressure xenoliths and associated Cenozoic basalts from Northeastern Tasmania

Abundant mantle xenoliths are found in widespread undersaturated Cenozoic basaltic rocks in Northeastern Tasmania and comprise lavas, dykes, plugs and diatremes. The basanites and nephelinites, include primitive magmas (11–14 wt.% MgO) with OIB-like geochemical features. Trace element and Pb– and Sr–Nd isotope data suggest that they were generated by mixing of melts derived from low degree (< 5%) melting of both garnet- (∼ 90%) and spinel lherzolite (∼ 10%) facies mantle sources with HIMU and EMII characteristics. The associated xenolith suite consists mainly of spinel lherzolite and rare spinel pyroxenite with predominantly granoblastic textures. Calculated oxygen fugacities indicate equilibration of the xenoliths at 0.81 to 2.65 log units below the fayalite–magnetite–quartz (FMQ) buffer. Mantle xenolith equilibration temperatures range from 890–1050 ± 50 °C at weakly constrained pressures between 0.8 and 11.5 GPa. A hot xenolith's geotherm is indicated and attributed to tectonothermal events associated with the break-up of Gondwanaland and/or the opening of the Tasman Sea.

Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, ∼8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite. A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe 85Ni 14Co 1) trapped within the glass beads indicates a log oxygen fugacity of −11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this f O2 corresponds to a minimum pressure of 41 MPa on the graphite–C–O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe–FeO activity model for the natural A17 orange glass–metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many lunar basalts and the ubiquitous Fe-metal in these rocks are also likely generated by the oxidation of carbon. The presence of carbon in the lunar basalts and the recent discovery of ppm levels of water in lunar basalts indicate that at least parts of the lunar interior still contained volatiles at 3.9 bybp.

Oxygen fugacity of the metasomatizing melt in a polymict peridotite from Kimberley

Kimberlitic melts are not only the transport vehicles for diamonds and mantle material to the Earth's surface but probably also one of the most common media responsible for mantle metasomatism in the subcontinental lithospheric mantle. We determined the Fe 2+/Fe 3+ in matrix and overgrowth garnets of a polymict breccia by electron microprobe and, from coexisting grt, opx and ol, calculated the oxygen fugacity of the melt which percolated, interacted and solidified this peridotite breccia. The percolating melt is inferred to be a Si-poor, Mg-rich and fluid-charged melt with a low Ca-activity, presumably of kimberlitic composition. The calculated oxygen fugacity is about 0.5 log units below the FMQ and just above the EMOG/D buffer at the likely conditions of solidification of the melt at around 1150 °C and 3.5 GPa. Such high oxygen fugacities would explain the common resorbed nature of diamonds from southern African occurrences if the transporting kimberlites of Cretaceous age were of a similar nature.

Metal–silicate partitioning of tungsten at high pressure and temperature: Implications for equilibrium core formation in Earth

Tungsten partitioning between liquid metal and liquid silicate, D(W), from 1723–2673 K, 0.5–18 GPa, and over a wide range of metal and silicate compositions provides constraints on planetary core formation models. We find that W partitioning is extremely sensitive to the carbon content of the metal alloy, becoming about an order of magnitude more siderophile at carbon saturation. Activity-composition corrections based on interactions between W–C and Fe–C in metal solution shift calculated D(W) to more lithophile values, and calculated oxygen fugacities ( fO 2) to more oxidizing values, than uncorrected data. W exists as a highly charged cation in silicate solution, displaying a mixture of oxidation states from + 4 to + 6 in experiments at fO 2 of ∼ 0.5–2 log units below the iron–wüstite buffer. At constant fO 2, the average calculated valence decreases with pressure from ∼ + 5.5 at 0.5 GPa to ∼ + 4 at 11–18 GPa. As a result of its high oxidation state, W partitioning is strongly dependent on silicate melt polymerization and fO 2. In contrast to some previous results, we find that D(W) may decrease slightly in response to increasing temperature in the pressure range of our experiments. Pressure exerts a non-monotonic effect: D(W) increases with pressure up to ∼ 3 to 4 GPa, but decreases at higher pressures. Previous models for the effects of pressure and temperature on W partitioning that conflict with our results appear to result from a conflation of the intensive parameters of pressure, temperature, and carbon content. The mantle abundance of W could have been set by single-stage metal–silicate equilibration along the liquidus in a deep peridotite magma ocean at pressures from 20–50 GPa, and at oxygen fugacities consistent with the mantle's present iron budget (IW− 2 to − 2.5). Equilibration at higher pressure is viable if the core-forming metal contained a significant, but not unreasonable, abundance of carbon (∼ 2 wt.%). Recent continuous accretion models involving multi-stage metal-silicate equilibration in a deepening magma ocean with progressive oxidation of the silicate remain permissible given our new treatment of W partitioning data.

Outgassing of ordinary chondritic material and some of its implications for the chemistry of asteroids, planets, and satellites

We used chemical equilibrium calculations to model thermal outgassing of ordinary chondritic material as a function of temperature, pressure, and bulk composition and use our results to discuss outgassing on asteroids and the early Earth. The calculations include ∼1000 solids and gases of the elements Al, C, Ca, Cl, Co, Cr, F, Fe, H, K, Mg, Mn, N, Na, Ni, O, P, S, Si, and Ti. The major outgassed volatiles from ordinary chondritic material are CH4, H2, H2O, N2, and NH3 (the latter at conditions where hydrous minerals form). Contrary to widely held assumptions, CO is never the major C-bearing gas during ordinary chondrite metamorphism. The calculated oxygen fugacity (partial pressure) of ordinary chondritic material is close to that of the quartz–fayalite–iron (QFI) buffer. Our results are insensitive to variable total pressure, variable volatile element abundances, and kinetic inhibition of C and N dissolution in Fe metal. Our results predict that Earth's early atmosphere contained CH4, H2, H2O, N2, and NH3; similar to that used in Miller—Urey synthesis of organic compounds.

Geochemistry and petrology of Tertiary volcanic rocks and related ultramafic xenoliths from the central and eastern Oman Mountains

The Tertiary volcanic rocks of the central and the eastern parts of the Oman Mountains consist mainly of basanites with abundant upper mantle ultramafic xenoliths. The lavas are alkaline (42–43 wt.% SiO 2; 3.5–5.5 wt.% Na 2O + K 2O). They include primitive (11–14 wt.% MgO) features with strong OIB-like geochemical signatures. Trace element and Sr–Nd isotope data for the basanites suggest mixing of melts derived from variable degrees of melting of both garnet- and spinel lherzolite-facies mantle source. The associated xenolith suite consists mainly of spinel and Cr-bearing diopside wehrlite, lherzolite and dunite with predominantly granuloblastic textures. No significant difference in chemistry was found between the basanites and xenoliths from the central and eastern Oman Mountains, which indicate a similar mantle source. Calculated oxygen fugacity indicates equilibration of the xenoliths at − 0.43 to − 2.2 log units above the fayalite–magnetite–quartz (FMQ) buffer. Mantle xenolith equilibration temperatures range from 910–1045 + 50 °C at weakly constrained pressures between 13 and 21 kbar. Xenolith data and geophysical studies indicate that the Moho is located at a depth of ∼ 40 km. A geotherm substantially hotter (90 mW m − 2 ) than the crust–mantle boundary (45 mW m − 2 ) is indicated and probably relates to tectonothermal events associated with the local and regional Tertiary magmatism. The petrogenesis of the Omani Tertiary basanites is explained by partial melting of an asthenospheric mantle protolith during an extension phase predating opening of the Gulf of Aden and plume-related alkaline volcanic rocks.

Mineralogy and petrology of the LaPaz Icefield lunar mare basaltic meteorites

Five basaltic meteorites from the LaPaz ice field are paired on the basis of their mineralogy and texture, and represent a unique basalt type distinct from those in the Apollo or Luna sample collections. LaPaz Icefield (LAP) 02205, LAP 02224, LAP 02226, LAP 02436 and LAP 03632 all contain plagioclase, pyroxene, ilmenite, spinel, olivine, and minor troilite, metal, phosphate, baddeleyite and silica (cristobalite). Brown glassy melt veins are ubiquitous and cross the primary igneous texture. Plagioclase, the major mineral and occurring as laths in a subophitic texture, is of narrow compositional range, from An85-89. Pyroxene, also a major mineral, is strongly zoned, from augite and pigeonite cores to very iron-rich rims. Ilmenite laths comprise approximately 3-5% of the basalts. Spinels show a large compositional range, comparable to that documented in Apollo 15 basalts, indicating an early chromite-rich stage followed by an intermediate to late stage with Cr-rich ulvspinel. Relatively large, subhedral to skeletal olivine crystals (Fo46-62) are sparse, and are too Forich to be in equilibrium with the bulk rock, indicating that these are xenocrysts rather than phenocrysts. The presence of melt veins with a similar composition to the bulk rock, maskelynitized plagioclase feldspar, and metastable cristobalite indicate that these rocks underwent significant shock, between 30 and 50 GPa. Calculated oxygen fugacity, using spinel-ilmenite-iron metal equilibria, is within the range defined by previous studies of lunar materials. The bulk composition (low MgO) and low calculated temperatures, together with modelling calculations, indicate an origin by fractional crystallization of a more primitive low TiO2 parent liquid similar to Apollo 12 olivine basalt.

Reduced carbonic fluids in mafic granulite xenoliths from the Bakony–Balaton Highland Volcanic Field, W-Hungary

Amphibole-bearing and amphibole-free garnet granulite xenoliths (clinopyroxene, plagioclase, garnet ± orthopyroxene, ± amphibole) from two localities of the Bakony–Balaton Highland Volcanic Field (Sabar-hegy and Szentbékkálla) were investigated by means of textural analysis, mineral chemistry, mineral equilibria, geothermobarometry and fluid inclusion studies. We have determined the P– T path of these lower crustal xenoliths, which begins at peak pressure between 0.9 and 1.4 GPa. The peak pressure was followed by temperature increase of about 200–300 °C and 0.3–0.7 GPa pressure decrease which is marked by breakdown reactions of garnet and pargasitic amphibole. Garnet broke down first to orthopyroxene–anorthite–spinel (type 1) then to olivine–plagioclase ± spinel (type 2) symplectite. Amphibole broke down to form clinopyroxene–plagioclase–Fe–Ti oxide-melt ± orthopyroxene ± olivine mineral assemblage. These changes in P– T conditions were caused by crustal thinning. The present day crustal thickness (max. 32 km) indicates that garnet granulites are no longer stable in the lower crust of the Pannonian Basin. The calculated crustal thinning factor is between 1.6 and 1.8 in accordance with the values calculated from tectonic methods. A unique CO 2–CO–C fluid system—which has not been described from the lower crust so far—occurs in inclusions of the rock-forming minerals, mainly in plagioclase and clinopyroxene. A primary and two secondary fluid inclusion (FI) generations were identified on the basis of textural analyses and distribution of homogenization temperatures. Primary FIs are connected to the formation of garnet granulite. The older secondary generation was trapped after the main temperature increase and some pressure decrease during crustal thinning. The younger secondary generation trapped within the depth limits of the present lower crust at pressures between 0.6–0.7 GPa. The overall composition of the fluid system has not changed during crustal thinning. The calculated oxygen fugacity values are slightly above and under QFM (between 10–8.5 and 10–10.1 at 1200 °C).

A Mössbauer study of pseudotachylytes: redox conditions during seismogenic faulting

The redox conditions during frictional melting provide information on the physical and chemical conditions during seismic slip in the crust. Here we examine frictional melts from five localities by analyzing host rocks and corresponding pseudotachylytes using Mossbauer spectroscopy. The faults examined are located at South Mountain, Arizona; Fort Foster, Maine (two localities); Long Ridge fault, North Carolina; and the Homestake shear zone, Colorado. The main iron-bearing phases in the pseudotachylytes are phyllosilicates (biotite, muscovite and clays) and iron oxides (magnetite and hematite) and minor pyrite. The ferrous/ferric ratios of the phyllosilicates in the host rocks are the same as those in the pseudotachylytes, except for the hematite-bearing pseudotachylyte from the Long Ridge fault, which is more oxidized. The magnetites in the host rocks and the corresponding pseudotachylytes have different ferric and ferrous iron distributions, which is attributed to different cation chemistry, rather than redox conditions. With the exception of the South Mountain locality, the ferric/ferrous ratios of the micas are interpreted to record the primary redox state of the pseudotachylyte melt as the calculated oxygen fugacities are consistent with magnetite and hematite equilibria. Pyrite-bearing pseudotachylytes plot ~0–1 log10 units above the fayalite-magnetite-quartz (FMQ) buffer. Magnetite-bearing pseudotachylytes plot ~2–4 log10 units above the FMQ buffer, and hematite-bearing pseudotachylytes plot 3.5 log10 units above the hematite-magnetite (HM) buffer. Hematite-bearing pseudotachylytes, together with previous oxygen isotope data, are inferred to represent melting in the presence of externally derived pressurized water. Other localities are inferred to represent melting under rock-buffered, closed system, conditions. If the localities studied are representative of seismogenic faulting, the calculated oxygen fugacities indicate that, in the system C–O–H–S, H2O and CO2 should be the dominant fluid species. This is the first detailed study of the redox state of pseudotachylytes.