Macrocryst Fe - Ti oxides in olivine melilitites from Namaqualand-Bushmanland South Africa

Ilmenite macrocrysts in olivine melilitites from Namaqualand-Bushmanland, South Africa, have decomposed by subsolidus reduction to form oriented Mg-titanomagnetite along {0001} ilmenite planes. Residual ilmenite contains 10–11 wt% MgO, 1 wt% MnO, and 0.1 wt% Cr₂O₃. This macrocryst assemblage is mantled by an annulus of Mg-titanomagnetite, followed by an overgrowth of radiating magnetite + perovskite. Terminal compositions of these magnetites are similar to groundmass spinels, and to the outermost margins of magnetite macrocrysts that have very high Fe³⁺ core contents. The assemblages are remarkably similar to oxide intergrowths in kimberlites and an upper mantle derivation is proposed for ilmenite macrocrysts in these melilitites. Oxidation states in the source regions are also very similar, whether on-or off-craton, being slightly above FMQ (NNO), but reduced to FMQWM with the onset of decompression, volatile loss, and carbonate immiscibility. In the case of the melilitites, late stage, low pressure crystallization above NNO precipated abundant magnetite + perovskite. The oxide fO₂ data are consistent with, and refine the fO₂ estimates obtained previously for the behavior of Fe/Mg and Ni contents in olivine from the same suite of samples.     

A hydrothermal investigation of the system FeOFe2O3TiO2: A discussion with new data

New experimental data on the system FeOFe₂O₂TiO₂ using a new oxygen buffer are presented. It is found that there is a narrow range of oxygen fugacity above 550°C within which hematite and ilmenite coexist stably.     

Oxidised phase relations of a primitive basalt from Grenada,Lesser Antilles

A series of liquidus determinations is reported for a primitive arc basalt (15.4 wt % MgO, 45.5 wt % SiO₂) from Grenada, Lesser Antilles, at anhydrous, H₂O-undersaturated and H₂O-saturated conditions in the pressure range 1 atm to 1.7 GPa. \(\hbox{Fe}^{3+}/\Upsigma\hbox{Fe}\) of high-pressure experimental glasses as measured by μXANES ranges from 0.44 to 0.86, corresponding to oxygen fugacities (fO₂) between 3.2 and 7.8 log units above the nickel–nickel oxide redox buffer (NNO). 1-atm experiments conducted from NNO ? 2.5 to + 3.8 show that increasing fO₂ mainly increases the forsterite content (Fo) of olivine and has little effect on phase relations. The crystallisation sequence at lower crustal pressures for all water contents is forsteritic olivine + Cr-rich spinel followed by clinopyroxene. The anhydrous liquidus is depressed by 100 and 120 °C in the presence of 2.9 and 3.8 wt % H₂O, respectively. H₂O-undersaturated experiments at NNO + 3.2 to + 4.5 produce olivine of equivalent composition to the most primitive olivine phenocrysts in Grenadan picrites (Fo_91.4). We conclude that direct mantle melts originating beneath Grenada could be as oxidised as ~NNO + 3, consistent with the uppermost estimates from olivine–spinel oxybarometry of high Mg basalts. μXANES analyses of olivine-bearing experimental glasses are used to develop a semi-empirical oxybarometer based on the value of \({{K}_{D}}_{\rm ol-melt}^{\rm Fe-Mg}\) when all Fe is assumed to be in the Fe²⁺ state (\({K}_{D}^{{\rm Fe}_T}\)). The oxybarometer is tested on an independent data set and is able to reproduce experimental fO₂ to ≤1.2 log units. Experiments also show that the geochemically and petrographically distinct M- and C-series lavas on the island can be produced from hydrous melting of a common picritic source. Low pressures expand the olivine stability field at the expense of clinopyroxene, enriching an evolving melt in CaO and forcing differentiation to take place along a C-series liquid line of descent. Higher pressure conditions allow early and abundant clinopyroxene crystallisation, rapidly depleting the melt in both CaO and MgO, and thus creating the M-series.     

Ilmenite composition in the Tellnes Fe–Ti deposit,SW Norway: fractional crystallization,postcumulus evolution and ilmenite–zircon relation

Major and trace element XRF and in situ LA-ICP-MS analyses of ilmenite in the Tellnes ilmenite deposit, Rogaland Anorthosite Province, SW Norway, constrains a two stage fractional crystallization model of a ferrodioritic Fe-Ti-P rich melt. Stage 1 is characterized by ilmenite-plagioclase cumulates, partly stored in the lower part of the ore body (Lower Central Zone, LCZ), and stage 2 by ilmenite-plagioclase-orthopyroxene-olivine cumulates (Upper Central Zone, UCZ). The concentration of V and Cr in ilmenite, corrected for the trapped liquid effect, (1) defines the cotectic proportion of ilmenite to be 17.5 wt% during stage 1, and (2) implies an increase of D _V^Ilm during stage 2, most likely related to a shift in fO₂. The proportion of 17.5 wt% is lower than the modal proportion of ilmenite (ca. 50 wt%) in the ore body, implying accumulation of ilmenite and flotation of plagioclase. The fraction of residual liquid left after crystallization of Tellnes cumulates is estimated at 0.6 and the flotation of plagioclase at 26 wt% of the initial melt mass. The increasing content of intercumulus magnetite with stratigraphic height, from 0 to ca. 3 wt%, results from differentiation of the trapped liquid towards magnetite saturation. The MgO content of ilmenite (1.4–4.4 wt%) is much lower than the expected cumulus composition. It shows extensive postcumulus re-equilibration with trapped liquid and ferromagnesian silicates, correlated with distance to the host anorthosite. The Zr content of ilmenite, provided by in situ analyses, is low (<114 ppm) and uncorrelated with stratigraphy or Cr content. The data demonstrate that zircon coronas observed around ilmenite formed by subsolidus exsolution of ZrO₂ from ilmenite. The U-Pb zircon age of 920 ± 3 Ma probably records this exsolution process. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystallization of quartz dioritic magmas at 2 and 1 kbar: experimental results

Crystallization experiments were performed on quartz diorite (~55 wt.% SiO₂, 3.1–8.4 wt.% MgO) from the G?siniec Intrusion (Bohemian Massif, SW Poland) at 1?2 kbar, 750–850°C, various mole fractions of water and with fO₂ buffered by the NNO buffer. The two natural quartz diorites (leucocratic poikilitic quartz diorite - ‘LPD’ and melanocratic quartz diorite - ‘MD’) differ in whole rock and mineral composition with MD being richer in MgO and poorer in CaO than LPD, probably due to accumulation of mafic minerals or melt removal in MD. LPD represents melt composition and is used to reconstruct crystallization conditions in the G?siniec Intrusion. The crystallization history of LPD magma, deduced from experimental and natural mineral compositions, includes a higher pressure stage probably followed by emplacement at ~2 kbar of partly crystallized magma at temperatures ~850?800°C and quick cooling. The mineral assemblage present in LPD requires water contents in the magma of at least 5 wt% and oxygen fugacity below that controlled by the NNO buffer. The compositions of mafic minerals in the MD composition were equilibrated at temperatures below 775°C and at subsolidus conditions. The equilibration was probably due to the reaction between water-rich, oxidizing residual melt and the cumulatic-restitic mineral assemblage. MD is characterized by occurrence of the euhedral cummingtonite and increasing anorthite content in the rims of plagioclase. A similar reaction was reproduced experimentally in both LPD and MD compositions indicating that cummingtonite may be a late magmatic phase in quartz dioritic systems, crystallizing very close to solidus and only from water saturated magma.     

Oxide and sulphide isograds along a Late Archean, deep-crustal profile in Tamil Nadu, south India

Oxide–sulphide–Fe–Mg–silicate and titanite–ilmenite textures as well as their mineral compositions have been studied in felsic and intermediate orthogneisses across an amphibolite (north) to granulite facies (south) traverse of lower Archean crust, Tamil Nadu, south India. Titanite is limited to the amphibolite facies terrane where it rims ilmenite or occurs as independent grains. Pyrite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade. Pyrrhotite is confined to the high‐grade granulites. Ilmenite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade and occurring primarily as hemo‐ilmenite in the high‐grade granulite facies rocks. Magnetite is widespread throughout the traverse and is commonly associated with ilmenite. It decreases in abundance with increasing metamorphic grade. In the granulite facies zone, reaction rims of magnetite + quartz occur along Fe–Mg silicate grain boundaries. Magnetite also commonly rims or is associated with pyrite. Both types of reaction rims represent an oxidation effect resulting from the partial subsolidus reduction of the hematite component in ilmenite to magnetite. This is confirmed by the presence of composite three oxide grains consisting of hematite, magnetite and ilmenite. Magnetite and magnetite–pyrite micro‐veins along silicate grain boundaries formed over a wide range of post‐peak metamorphic temperatures and pressures ranging from high‐grade SO₂ to low‐grade H₂S‐dominated conditions. Oxygen fugacities estimated from the orthopyroxene–magnetite–quartz, orthopyroxene–hematite–quartz, and magnetite–hematite buffers average 2.5 log units above QFM. It is proposed that the trends in mineral assemblages, textures and composition are the result of an external, infiltrating concentrated brine containing an oxidizing component such as CaSO₄ during high‐grade metamorphism later acted upon by prograde and retrograde mineral reactions that do not involve an externally derived fluid phase.     

Divergent T–ƒO<Subscript>2</Subscript> paths during crystallisation of H<Subscript>2</Subscript>O-rich and H<Subscript>2</Subscript>O-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–?O₂ 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–?O₂ 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 ?O₂ 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 ?O₂?≈?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.     

Oxide–sulphide relationships in sodalite-bearing metasomatites of the Epembe–Swartbooisdrif Alkaline Province, north-west Namibia

The south-eastern part of Kunene Intrusive Complex (KIC), Namibia/Angola, is host to volumetrically significant, and economically important, concentrations of sodalite in the area around Swartbooisdrif, north-west Namibia. The mineralisation was formed by metasomatic exchange with carbonatites of the Epembe–Swartbooisdrif Alkaline Province. This process led to the breakdown of ore minerals initially present in various rock types of the KIC and caused the formation of new opaque phases in the sodalite-bearing metasomatites. A detailed investigation of textures and chemical compositions of the Fe–Ti oxides and sulphides has allowed evaluation of the complex ore-forming processes related to the polyphase magmatic and metasomatic history of the sodalite deposit. The predominant opaque phases in the various rock types of the KIC are ilmenite and (titano)magnetite, which are highly concentrated in the so-called magnetite plugs. It is clear from the textural evidence that most of the ilmenite and (titano)magnetite, although of orthomagmatic origin, recrystallised under subsolidus conditions. Conformably, their respective chemical compositions and phase relations represented in the system FeO–1/2Fe₂O₃–TiO₂ point to re-equilibration at temperatures below 600 °C. Ilmenite and (titano)magnetite were affected by later deformation and decomposed by various reactions, related to, or outlasting, the metasomatic process. Oxidation of ilmenite led to the formation of symplectitic aggregates of rutile and secondary magnetite. Carbonatisation of the Fe–Ti oxides produced rutile and the siderite and rhodochrosite components in ankerite. Pyrite, in part together with rutile and secondary magnetite, was formed by sulphidation of the Fe–Ti oxides. Conspicuous aggregates of granular or lamellar intergrowths of pyrite with hematite and/or magnetite are interpreted as products of contemporaneous sulphidation and oxidation of former igneous pyrrhotite. Rarely observed pyrrhotite with pentlandite lamellae is probably not an igneous relic, but was formed during the metasomatic event. Smaller amounts of chalcopyrite, bornite, digenite–chalcocite, galena, ferroan siegenite, millerite and polydymite testify to different cooling stages during or after metasomatism. Applying the phase relations in the simplified system Fe–Co–Ni–S–O, we were able to reconstruct a semi-quantitative T–f(S₂)–f(O₂) path for the ore-forming processes. Received: 22 October 1998 / Accepted: 27 October 1999     

Chemical Composition of Rock-Forming Minerals in Copper–Gold-Bearing Tonalite Porphyries at the Batu Hijau Deposit, Sumbawa Island, Indonesia: Implications for Crystallization Conditions and Fluorine–Chlorine Fugacity

Copper–gold mineralization at the world‐class Batu Hijau porphyry deposit, Sumbawa Island, Indonesia, is closely related to the emplacement of multiple stages of tonalite porphyries. Petrographic examination indicates that at least two texturally distinct types of tonalite porphyries are currently recognized in the deposit, which are designated as “intermediate tonalite” and “young tonalite”. They are mineralogically identical, consisting of phenocrysts of plagioclase, hornblende, quartz, biotite and magnetite ± ilmenite, which are set in a medium‐coarse grained groundmass of plagioclase and quartz. The chemical composition of the rock‐forming minerals, including plagioclase, hornblende, biotite, magnetite and ilmenite in the tonalite porphyries was systematically analyzed by electron microprobe. The chemical data of these minerals were used to constrain the crystallization conditions and fluorine–chlorine fugacity of the corresponding tonalitic magma during its emplacement and crystallization. The crystallization conditions, including temperature (T), pressure (P) and oxygen fugacity (fO₂), were calculated by applying the hornblende–plagioclase and magnetite–ilmenite thermometers and the Al‐in‐hornblende barometer. The thermobarometric data indicate that the tonalite porphyries were emplaced at 764 ± 22°C and 1.5 ± 0.3 × 10⁵ kPa. If the pressure is assumed to be lithostatic, it is interpreted that the rim of hornblende and plagioclase phenocrysts crystallized at depths of approximately 5.5 km. As estimated from magnetite–ilmenite thermometry, the subsolidus conditions of the tonalite intrusion occurred at temperatures of 540–590°C and log fO₂ ranging from ?20 to ?15 (between Ni‐NiO and hematite–magnetite buffers). This occurred at relatively high fO₂ (oxidizing) condition. The fluorine–chlorine fugacity in the magma during crystallization was determined on the basis of the chemical composition of magmatic biotite. The calculation indicates that the fluorine–chlorine fugacity, represented by log (fH₂O)/(fHF) and (fH₂O)/(fHCl) in the corresponding tonalitic magma range from 4.31 to 4.63 and 3.62 to 3.79, respectively. The chlorine fugacity (HCl) to water (H₂O) is relatively higher than the fluorine fugacity (HF to water), reflecting a high activity of chlorine in the tonalitic magma during crystallization. The relatively higher activity of chlorine (rather than fluorine) may indicate the significant role of chloride complexes (CuCl₂^? and AuCl₂^?) in transporting and precipitating copper and gold at the Batu Hijau deposit.     

Hydration vs. oxidation: Modelling implications for Fe–Ti oxide crystallisation in mafic intrusions, with specific reference to the Panzhihua intrusion, SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion:（1） low-Ti,high CaO and low H₂O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H₂O（>1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ + 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O₂） and H₂O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H₂O contents（0.5-1 wt.%） but at the lower end of TiO₂ content for typical high-Ti basalts（2.5 wt.%TiO₂）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H₂O may be responsible for changing the crystallisation path.An increase in H₂O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H₂O then results in precipitation of Mt-Uv alone. The H₂O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H₂O alters the crystallisation sequence of the basaltic magmas so that at high H₂O and f（O₂） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H₂O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.     

Vermicular orthopyroxene-magnetite symplectites from the Wateranga layered mafic intrusion,Queensland, Australia

Orthopyroxene-magnetite intergrowths (symplectites), partly or completely surrounding olivine, are described from the Wateranga layered mafic intrusion, Queensland, Australia. The texture occurs in unmetamorphosed plagioclase-rich norites, olivine gabbros and troctolites in which the primary minerals are olivine (Fo_63–69) orthopyroxene (En_66–72), clinopyroxene (Wo₄₂En₄₂Fs₁₆), plagioclase (An_49–65), hornblende, ilmenite, magnetite and sulphides. Symplectites range from incipient fine grained developments around corroded olivine grains to intricately formed pseudomorphs after olivine and slow a consistent orthopyroxene/magnetite ratio. Orthopyroxene in symplectites is commonly in optical continuity with surrounding magnetite-free orthopyroxene rims. Later intercumulus hornblended has replaced orthopyroxene. There is marked chemical similarity between primary and simplectite, orthopyroxenes and magnetites. Textures similar to those described here are considered elsewhere to have formed at a late magmatic stage or by solid state reactions involving subsolidus oxidation of olivine. In the Wateranga intrusion textural relations, the chemical similarity between primary and symplectite phases, and the consistent volume proportions of magnetite and orthopyroxene in the intergrowths suggest that they developed during late magmatic crystallization.     

Postcumulus modification of magnetite grains in the upper zone of the Bushveld Complex,South Africa

A detailed electron microprobe study has been made of magnetite grains from magnetitite layer 1 of the upper zone of the Bushveld Complex, in order to establish if there is any evidence for postcumulus processes having affected magnetite compositions. Representative composition profiles obtained from detailed step traverses are presented for touching magnetite grains and where magnetite is in contact with either ilmenite or plagioclase.Magnetite grains in all textural settings are compositionally heterogeneous. Touching magnetite grains display systematic compositional zonations: the rims of grains show a marked decrease in Al and Mg towards the grain boundary; the cores are characterised by a distinctive peak and trough pattern for these elements. These variations can be related to the positions of exsolved phases. Exsolutions in the cores are either pleonaste or an Fe³⁺ bearing AlMg spinel, whereas those at the grain boundaries are generally more Al-rich and include corundum. Similar exsolution related compositional variations for Mg and Al were found in magnetites in contact with ilmenite and plagioclase.A model has been developed which illustrates the possible sequence of postcumulus events during the interval between accumulation of the magnetite and the cessation of subsolidus reactions. The essential feature of the model is the delicate interplay between depletion of the host magnetite by corundum, pleonaste and the Fe³⁺ bearing AlMg spinel exsolutions, and diffusion of Al and Mg into the depleted areas from the surrounding magnetite.Data for Cr contents in magnetites show that although this particular trace element is apparently resistant to redistribution by exsolution processes, it is affected by subsolidus re-equilibration between magnetite and ilmenite, or magnetite and intercumulus liquid.     

Sixty thousand years of magmatic volatile history before the caldera-forming eruption of Mount Mazama, Crater Lake, Oregon

The well-documented eruptive history of Mount Mazama, Oregon, provides an excellent opportunity to use pre-eruptive volatile concentrations to study the growth of an explosive silicic magmatic system. Melt inclusions (MI) hosted in pyroxene and plagioclase crystals from eight dacitic–rhyodacitic eruptive deposits (71–7.7?ka) were analyzed to determine variations in volatile-element concentrations and changes in magma storage conditions leading up to and including the climactic eruption of Crater Lake caldera. Temperatures (Fe–Ti oxides) increased through the series of dacites, then decreased, and increased again through the rhyodacites (918–968 to ~950 to 845–895?°C). Oxygen fugacity began at nickel–nickel-oxide buffer (NNO) +0.8 (71?ka), dropped slightly to NNO +0.3, and then climbed to its highest value with the climactic eruption (7.7?ka) at NNO +1.1 log units. In parallel with oxidation state, maximum MI sulfur concentrations were high early in the eruptive sequence (~500?ppm), decreased (to ~200?ppm), and then increased again with the climactic eruption (~500?ppm). Maximum MI sulfur correlates with the Sr content (as a proxy for LREE, Ba, Rb, P₂O₅) of recharge magmas, represented by basaltic andesitic to andesitic enclaves and similar-aged lavas. These results suggest that oxidized Sr-rich recharge magmas dominated early and late in the development of the pre-climactic dacite–rhyodacite system. Dissolved H₂O concentrations in MI do not, however, correlate with these changes in dominant recharge magma, instead recording vapor solubility relations in the developing shallow magma storage and conduit region. Dissolved H₂O concentrations form two populations through time: the first at 3–4.6 wt% (with a few extreme values up to 6.1 wt%) and the second at ≤2.4 wt%. CO₂ concentrations measured in a subset of these inclusions reach up to 240?ppm in early-erupted deposits (71?ka) and are below detection in climactic deposits (7.7?ka). Combined H₂O and CO₂ concentrations and solubility models indicate a dominant storage region at 4–7?km (up to 12?km), with drier inclusions that diffusively re-equilibrated and/or were trapped at shallower depths. Boron and Cl (except in the climactic deposit) largely remained in the melt, suggesting vapor–melt partition coefficients and gas fractions were low. Modeled Li, F, and S vapor–melt partition coefficients are higher than those of B and Cl. The decrease in maximum MI CO₂ concentration following the earliest dacitic eruptions is interpreted to result from a broadening of the shallow storage region to greater than the diameter of subjacent feeders, so that greater proportions of reservoir magma were to the side of CO₂-bearing vapor bubbles ascending vertically from the locus of recharge magma injection, thereby escaping recarbonation by streaming vapor bubbles. The Mazama melt inclusions provide a picture of a growing magma storage region, where chemical variations in melt and magma occur due to changes in the nature and supply rate of magma recharge, the timing of degassing, and the possible degree of equilibration with gases from below.     

Oxygen fugacity control in piston-cylinder experiments

The main goal of this study was to develop and test a capsule assembly for use in piston-cylinder experiments where oxygen fugacity could be controlled in the vicinity of the QFM buffer without H₂O loss or carbon contamination of the sample material. The assembly consists of an outer Pt-capsule containing a solid buffer (Ni–NiO or Co–CoO) plus H₂O and an inner AuPd-capsule, containing the sample, H₂O and a Pt-wire. No H₂O loss is observed from the sample, even after 48 h, but a slight increase in H₂O content is found in longer runs due to oxygen and hydrogen diffusion into the AuPd-capsule. Oxygen fugacity of runs in equilibrium with the Ni–NiO (NNO) and Co–CoO (CoCO) buffers was measured by analyzing Fe dissolved in the Pt-wire and in the AuPd-capsule. The second method gives values that are in good agreement with established buffer values, whereas results from the first method are one half to one log units higher than the established values.     

A statistical-chemical and thermodynamic approach to the study of lunar mineralogy

Principal components analysis is used to study the chemical compositions of pyroxenes of five Apollo 12 specimens. Important correlations recognized in the variation of oxide weight per cent are: MGO, Al₂O₃, SiO₂| CaO, TiO₂, FeO MgO, Al₂O₃, SiO₂| FeO MgO, SiO₂, FeO | Al₂O₃, CaO, TiO₂ where the oxides on one side of the bar are correlated positively with each other and negatively with the oxides on the other side. Several other similarly distinct relationships with significantly less variance could be noted. These correlations indicating substitutional relationships can be interpreted as representative of stable and metastable trends of crystallization by using crystal-chemical and thermodynamic information. The per cent variance of pyroxene groups with characteristic trends in each specimen can be evaluated and interpreted in terms of history of crystallization. Distribution of Fe and Mg in certain pairs of olivine and pyroxene, which are found in contact in the rock and which may have crystallized simultaneously, is useful in recognizing the tendency towards chemical equilibrium in FeMg distribution during a limited interval in the liquidus or subsolidus stages.     

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}}}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 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 ulv?spinel 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 Ilm_50–80, 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 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.     

Vanadium partitioning between orthopyroxene,spinel and silicate melt and the redox states of mantle source regions for primary magmas

The partitioning of V between orthopyroxene-liquid and spinel-liquid has been investigated in synthetic and natural mafic and ultramafic compositions as a function of temperature and oxygen fugacity (fO₂) at 100 kPa and in one experiment at higher pressure. The purpose of the experiments was to understand redox relationships for V in silicate melts with a view to deriving an empirical oxygen barometer for geochemically altered mafic and ultramafic magmas in the geologic record. Partitioning data for both orthopyroxene-liquid and spinel-liquid show profound changes at an fO₂ approximately 3 orders of magnitude below the nickel-nickel oxide (NNO) buffer, suggesting changes in the dominant valence state of V in silicate liquids from V³⁺ to V⁴⁺, near this fO₂.The results of the experiments on orthopyroxene-liquid are combined with published data for olivine-liquid and are applied to suites of mafic and ultramafic magmas that have equilibrated with a harzburgite residue in the mantle. The results show that Archean alumina-undepleted komatiites could have formed at fairly high oxygen fugacities, near ΔNNO ∼ 0, somewhat higher than Cretaceous komatiites and related picrites in the Caribbean region (between ΔNNO ∼ −1 to −3), and plume-related picrites from West Greenland (ΔNNO ∼ − 3). Picrites and boninites from convergent margins record the highest fO₂’s by this method, (ΔNNO = +1 to +2), consistent with other petrological estimates of their redox states. The approach developed in this study can thus provide estimates for the redox states of altered, mantle-derived magmas in the geological record, to which more conventional methods of oxygen barometry cannot be applied.     

Reactions governing the chemistry of crater fumaroles from Vulcano Island,Italy, and implications for volcanic surveillance

More than 200 chemical and isotope analyses of fumarolic fluids collected at the Fossa Grande crater, Vulcano Island, during the 1980s show that the main process controlling these fluids is mixing between the gas released by a magma body and the vapour produced through evaporation of brines of marine origin. Large variations in the relative contribution of these two sources have been observed during the last 10 a. The main species (H₂O and CO₂), the inert gases (He and N₂), and the D content of steam are fixed by the mixing processes; they are therefore the best tracers the fraction of the deep magmatic component in the fumarolic fluids discharged at the surface. In contrast, the “fast” species (H₂ and CO) equilibrate at T,P values close to the outlet temperature and atmospheric pressure, and under redox conditions governed by the SO₂H₂S buffer, as indicated by thermodynamic calculations.Acid gases (HCl, HF, H₂S and SO₂) are partly contributed by the magmatic component and partly produced by the reactions between hot rocks, steam and salts which take place in the “dry” zones surrounding the central magmatic gas column, as suggested by the good agreement between their analytical and theoretical contents.     

Experimental constraints on the storage conditions of phonolites from the Kerguelen Archipelago

Phase relations of a phonolite (K1) and a tephri-phonolite (K2) from the Upper Miocene lavas in the Southeast Province of the Kerguelen Archipelago have been investigated in the P/T range 100–500 MPa and 700–900 °C at two fO₂ conditions (~ NNO and ~ NNO+2.3) to clarify the differentiation and pre-eruptive conditions of these magmas. Crystallization experiments were performed in cold seal pressure vessels (CSPV) and internally heated pressure vessels (IHPV) at various X_H2O, under reducing (log fO₂ ~ NNO) and oxidizing conditions (log fO₂ ~ NNO+2.3). Under reducing conditions, the resulting phase assemblage for K1 was: titanomagnetite, nepheline, alkali feldspar, clinopyroxene and biotite; under oxidizing conditions, the assemblage was: magnetite, plagioclase, alkali feldspar, nepheline, titanite (minerals given in the order of appearance with decreasing T at 200 MPa for 4 wt% water in the melt). It is emphasized that an effect of fO₂ on the phase stability of feldspars and feldspathoides was observed. Comparison of the natural and experimental phase assemblages shows that the pre-eruptive conditions for K1 must have been in the log fO₂ range NNO+1–NNO+2, at pressures above 200–250 MPa. Assuming a temperature of 800 °C, the water content of the melt is constrained to be between 4 and 6 wt% H₂O. The pre-eruptive fO₂ conditions for the less evolved sample K2 are more oxidizing with log fO₂ close to NNO+2.3. The experimental results show that the enrichment of alkalis in residual melts during differentiation of tephri-phonolites is enhanced at high fO₂.Editorial responsibility: J. Hoefs     

Accessory Fe-Ti oxides in the West-Carpathian I-type granitoids: witnesses of the granite mixing and late oxidation processes

Fe-Ti-oxides may reach hundreds ppm in I-type granitoids and close to microgranular mafic enclaves (MME) up to several thousands ppm. Western Carpathian I-type granitoids have magnetic susceptibility above 3?×?10^?4 SI units, whereas S-type granites are lower. Associated MMEs reach up to 160?×?10^?4 SI. The measurement of magnetic susceptibility in field appears a useful tool for regional mapping of I-type granites and searching enclaves. The increased contents of Fe-oxides around MME within host I-type granitoids are interpreted as result of hybridization with mafic magma. The hybridisation is manifested by occurrence of two Fe-Ti-oxide generations: (1) orthomagmatic titanomagnetite from pre-mixing stage, (2) late-magmatic magnetite of post-mixing stage. The titanomagnetites show composite textures with exsolved ilmenite. The oxybarometry (Sauerzapf et al. 2008; Ghiorso Evans 2009) yields temperatures 700?C750°C at fO₂ about NNO, and 650?C700°C below FMQ, respectively. Post-mixing pure magnetites originated from early titanomagnetite, annite and anorthite associated with titanite and apatite. The late oxidation seems to be responsible for high magnetic susceptibility of metaluminous I-type tonalites. Both post- and pre- mixing Fe-Ti oxides are locally converted to hematite.