The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

Divergent T-fO2 paths during crystallisation of H2O-rich and H2O-poor magmas as recorded by Ce and U in zircon, with implications for TitaniQ and TitaniZ geothermometry

During solidification of magma chambers as systems closed to chemical exchange with environs, the residual siliceous melt may follow a trend of rising, constant, or decreasing oxidation state, relative to reference buffers such as nickel + nickel oxide (NNO) or fayalite + magnetite + quartz. Titanomagnetite–hemoilmenite thermometry and oxybarometry on quenched volcanic suites yield temperature versus oxygen fugacity arrays of varied positive and negative slopes, the validity of which has been disputed for several years. We resolve the controversy by introducing a new recorder of magmatic redox evolution employing temperature- and redox-sensitive trace-element abundances in zircon. The zircon/melt partition coefficients of cerium and uranium vary oppositely in response to variation of magma redox state, but vary in tandem as temperature varies. Plots of U/Pr versus Ce4+/Ce3+ in zircon provide a robust test for change in oxidation state of the melt during zircon crystallisation from cooling magma, and the plots discriminate thermally induced from redox-induced variation of Ce4+/Ce3+ in zircon. Temperature-dependent lattice strain causes Ce4+/Ce3+ in zircon to increase strongly as zircon crystallises from cooling magma at constant Ce4+/Ce3+ ratio in the melt. We examine 19 zircon populations from igneous complexes in varied tectonic settings. Variation of zircon Ce4+/Ce3+ due to minor variation in melt oxidation state during crystallisation is resolvable in 11 cases but very subordinate to temperature dependence. In many zircon populations described in published literature, there is no resolvable change in redox state of the melt during tenfold variation of Ce4+/Ce3+ in zircons. Varied magmatic redox trends indicated by different slopes on plots of zircon U/Pr versus Ce4+/Ce3+ are corroborated by Fe–Ti-oxide-based T–ƒO2 trends of correspondingly varied slopes. Zircon and Fe–Ti-oxide compositions agree that exceptionally, H2O-rich arc magmas tend to follow a trend of rising oxidation state of the melt during late stages of fluid-saturated magmatic differentiation at upper-crustal pressures. We suggest that H2 and/or SO3 and/or Fe2+ loss from the melt to segregating fluid is largely responsible. Conversely, zircon and Fe–Ti-oxide compositions agree in indicating that H2O-poor magmas tend to follow a T–ƒO2 trend of decreasing oxidation state of the melt during late stages of magmatic differentiation at upper-crustal pressures, because the precipitating mineral assemblage has higher Fe3+/Fe2+ than coexisting rhyolitic melt. We present new evidence showing that the Fe–Ti-oxide oxybarometer calibration by Ghiorso and Evans (Am J Sci 308(9):957–1039, 2008) retrieves experimentally imposed values of ƒO2 in laboratory syntheses of Fe–Ti-oxide pairs to a precision of ± 0.2 log unit, over a large experimental temperature range, without systematic bias up to at least log ƒO2 ≈ NNO + 4.4. Their titanomagnetite–hemoilmenite geothermometer calibration has large systematic errors in application to Ti-poor oxides that precipitate from very oxidised magmas. A key outcome is validation of Fe–Ti-oxide-based values of melt TiO2 activity for use in Ti-in-zircon thermometry and Ti-in-quartz thermobarometry.We thank Paul Agnew and Alan Kobussen of Rio Tinto Exploration for financial support and for authorisation to publish research results. Additional financial support was provided by the ARC Centre of Excellence for Core to Crust Fluid Systems Grant CE110001017. MLF acknowledges the support of the Australian Research Council through the Future Fellowship Grant scheme (FT110100241). MLF also acknowledges support from the Australian Research Council through Linkage Project LP120100668. BDR acknowledges WMC Resources Ltd for financial support of his PhD research. RRL thanks the University of Bristol for a Benjamin Meaker Visiting Professorship which afforded an opportunity to clarify his understanding of this material through discussions with Professors Jon Blundy and Chris Hawkesworth

Experimental determination of coexisting iron–titanium oxides in the systems FeTiAlO, FeTiAlMgO, FeTiAlMnO, and FeTiAlMgMnO at 800 and 900°C, 1–4 kbar, and relatively high oxygen fugacity

A synthetic, low-melting rhyolite composition containing TiO2 and iron oxide, with further separate additions of MgO, MnO, and MgO + MnO, was used in hydrothermal experiments to crystallize Ilm-Hem and Usp-Mt solid solutions at 800 and 900°C under redox conditions slightly below nickel–nickel oxide (NNO) to $$\approx 3\,\log_{10} f_{{{\text{O}}_{2}}}$$ units above the NNO oxygen buffer. These experiments provide calibration of the FeTi-oxide thermometer + oxygen barometer at conditions of temperature and oxygen fugacity poorly covered by previous equilibrium experiments. Isotherms for our data in Roozeboom diagrams of projected %usp vs. %ilm show a change in slope at ≈ 60% ilm, consistent with the second-order transition from FeTi-ordered Ilm to FeTi-disordered Ilm-Hem. This feature of the system accounts for some, but not all, of the differences from earlier thermodynamic calibrations of the thermobarometer. In rhyolite containing 1.0 wt.% MgO, 0.8 wt.% MnO, or MgO + MnO, Usp-Mt crystallized with up to 14% of aluminate components, and Ilm-Hem crystallized with up to 13% geikielite component and 17% pyrophanite component. Relative to the FeTiAlO system, these components displace the ferrite components in Usp-Mt, and the hematite component in Ilm-Hem. As a result, projected contents of ulvöspinel and ilmenite are increased. These changes are attributed to increased non-ideality along joins from end-member hematite and magnetite to their respective Mg- and Mn-bearing titanate and aluminate end-members. The compositional shifts are most pronounced in Ilm-Hem in the range Ilm50–80, a solvus region where the chemical potentials of the hematite and ilmenite components are nearly independent of composition. The solvus gap widens with addition of Mg and even further with Mn. The Bacon–Hirschmann correlation of Mg/Mn in Usp-Mt and coexisting Ilm-Hem is displaced toward increasing Mg/Mn in ilmenite with passage from ordered ilmenite to disordered hematite. Orthopyroxene and biotite crystallized in experiments with added MgO and MgO + MnO; their X Fe varies with $$\log_{10} f_{{{\text{O}}_{2}}}$$ and T consistent with equilibria among ferrosilite, annite, and ferrite components, and the chemical potentials of SiO2 and orthoclase in the liquid. Experimental equilibration rates increased in the order: Opx < Bt < Ilm-Hem < Usp-Mag

Syvä avoin varasto ja matala suljettu kuljetussysteemi laakiobasalttisekvenssille paljastui Magmakammiosimulaattorin avulla

Karoo continental flood basalt (CFB) province is known for its highly variable trace element and isotopic composition, often attributed to the involvement of continental lithospheric sources. Here, we report oxygen isotopic compositions measured with secondary ion mass spectrometry for hand-picked olivine phenocrysts from similar to 190 to 180 Ma CFBs and intrusive rocks from Vestfjella, western Dronning Maud Land, that form an Antarctic extension of the Karoo province. The Vestfjella lavas exhibit heterogeneous trace element and radiogenic isotope compositions (e.g., epsilon(Nd) from -16 to +2 at 180 Ma) and the involvement of continental lithospheric mantle and/or crust in their petrogenesis has previously been suggested. Importantly, our sample set also includes rare primitive dikes that have been derived from depleted asthenospheric mantle sources (epsilon(Nd) up to + 8 at 180 Ma). The majority of the oxygen isotopic compositions of the olivines from these dike rocks (delta O-18 = 4.4-5.2%; Fo = 78-92 mol%) are also compatible with such sources. The olivine phenocrysts in the lavas, however, are characterized by notably higher delta O-18 (6.2-7.5%; Fo = 70-88 mol%); and one of the dike samples gives intermediate compositions (5.2-6.1%, Fo = 83-87 mol%) between the other dikes and the CFBs. The oxygen isotopic compositions do not correlate with radiogenic isotope compositions susceptible to crustal assimilation (Sr, Nd, and Pb) or with geochemical indicators of pyroxene-rich mantle sources. Instead, delta O-18 correlates positively with enrichments in large-ion lithophile elements (especially K) and Os-187. We suggest that the oxygen isotopic compositions of the Vestfjella CFB olivines primarily record large-scale subduction-related metasomatism of the sub-Gondwanan mantle (base of the lithosphere or deeper) prior to Karoo magmatism. The overall influence of such sources to Karoo magmatism is not known, but, in addition to continental lithosphere, they may be responsible for some of the geochemical heterogeneity observed in the CFBs.Peer reviewe

On the generation of isotopic disequilibrium during crustal anatexis of ancient metasedimentary and granitic rocks

Partial melting of rocks may lead to the generation of melts in isotopic disequilibrium with their source rocks. To examine the amount of disequilibrium created during anatexis in the Sr, Nd, and Pb isotopic systems, a model was producing using results of partial melt experiments to constrain the breakdown of major minerals during melting. Experimentally derived mineral dissolution equations were employed to account for contributions from accessory phases. Based upon results from this study, partial melts, especially from ancient rocks, are likely to be in considerable disequilibrium. The behavior of important accessory minerals during anatexis appears to exert considerable control over the magnitude of disequilibrium. The results of this work may have important implications for models of mass transfer during magmatism and for reconstructing temperature-time scales during episodes of crustal heating

Experimental petrology constraints on the recycling of mafic cumulate:a focus on Cr-spinel from the Rum Eastern Layered Intrusion, Scotland

Reactive liquid flow is a common process in layered intrusions and more generally in episodically refilled magma chambers. Interaction between newly injected melt and cumulates, or crystal mushes, perturbs the liquid line of descent of the melt and modifies mineral chemistry and texture. We present insights into the effects of assimilation of mafic cumulate rocks (gabbro, troctolite) by cogenetic Mg-rich basalt liquid using one-atmosphere, controlled fO2 phase equilibrium experiments on picritic parental liquid to the Rum layered intrusion, Scotland. For picrite-only experiments at fO2 = QFM, Cr-spinel (Cr# = Cr/[Cr + Al + Fe3+] = 0.43; Fe# = Fe2+/[Mg + Fe2+] = 0.32) saturates at 1320 °C, olivine (Fo88) at ~1290 °C, plagioclase (An77) at 1200 °C, and clinopyroxene (Mg#: 0.81) at 1180 °C. In melting experiments on picrite + gabbro mixtures, plagioclase (1230 °C, An80) and clinopyroxene (1200 °C, Mg#: 0.85) saturation temperature and mode are increased significantly. Cr-spinel in these experiments has a distinctive, low Fe#. In melting experiments on picrite + troctolite mixtures, plagioclase (An86) saturates at 1240 °C and clinopyroxene (Mg#: 0.81) at 1170 °C. Al-rich spinel crystallizes at high temperature (>1220 °C) and becomes more Cr-rich upon cooling, reaching the highest Cr# = 0.47 at 1180 °C (0.54 at QFM-1.2). The experimental results confirm that plagioclase and clinopyroxene stability plays a major role in determining the composition of coexisting spinel. Comparing our experimental results to the Rum Eastern Layered Intrusion, we propose a model for the precipitation of spinel from picrite–troctolite hybrid melt that is compatible with the observed olivine, plagioclase, and clinopyroxene chemistry.ISSN:0010-7999ISSN:1432-096

Peralkaline felsic magmatism at the Nemrut volcano, Turkey: impact of volcanism on the evolution of Lake Van (Anatolia) IV

Nemrut volcano, adjacent to Lake Van (Turkey), is one of the most important peralkaline silicic centres in the world, where magmatism for ~570,000 years has been dominated by peralkaline trachytes and rhyolites. Using onshore and Lake Van drill site tephra samples, we document the phenocryst and glass matrix compositions, confirming a complete spectrum from very rare mafic to dominantly silicic magmas. Magma mixing has been common and, along with the multi-lineage nature of the magmas, indicates that Nemrut has been a very open system where, nevertheless, compositionally zoned caps developed during periods of relative eruptive quiescence. Geothermometry suggests that the intermediate-silicic magmas evolved in an upper crustal magma reservoir at temperatures between 1100 and 750 °C, at fO2 close to the FMQ buffer. The silicic magmas either were halogen poor or exsolved a halogen-rich phase prior to or during eruption. An unusual Pb-rich phase, with up to 98.78 wt% PbO, is interpreted as having exsolved from the intermediate-rhyolitic magmas