V oxidation state in Fe–Ti oxides by high-energy resolution fluorescence-detected X-ray absorption spectroscopy

The oxidation state of vanadium in natural and synthetic Fe–Ti oxides is determined using high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS). Eleven natural magnetite-bearing samples from a borehole of the Main Magnetite Layer of the Bushveld Complex (South Africa), five synthetic Fe oxide samples, and three natural hematite-bearing samples from Dharwar supergroup (India) are investigated. V K edge spectra were recorded on the ID26 beamline at the European Synchrotron Radiation Facility (Grenoble, France), and the pre-edge features were used to determine the local environment and oxidation state of vanadium. In the case of the magnetite samples (natural and synthetic), we show that vanadium is incorporated in the octahedral site of the spinel structure under two oxidation states: +III and +IV. The variations of the pre-edge area are interpreted as various proportions in V³⁺ and V⁴⁺ (between 9.5 and 16.3% of V⁴⁺), V³⁺ being the main oxidation state. In particular, the variations of the V⁴⁺/V³⁺ ratio along the profile of the Main Magnetite Layer seem to follow the crystallization sequence of the layer. In the case of the hematite samples from India, the pre-edge features indicate that vanadium is substituted to Fe and mainly incorporated as V⁴⁺ (between 40 and 72% of V⁴⁺). We also demonstrate the potentiality of HERFD-XAS for mineralogical studies, since it can filter out the unwanted fluorescence and give better resolved spectra than conventional XAS.     

New calibration data for the Fe–Ti oxide thermo-oxybarometers from experiments in the Fe–Ti–O system at 1 bar, 1,000–1,300°C and a large range of oxygen fugacities

The current formulations of the Fe–Ti oxide thermobarometer (titanomagnetite–ilmenite_ss) fail to reproduce experimental results, in particular at the high temperatures that are relevant for basaltic assemblages. With the aim of improving the experimental basis of the calibration in the Fe–Ti–O system, we have synthesised assemblages of titanomagnetite–ilmenite_ss (Tmt–Ilm_ss), ilmenite_ss–pseudobrookite_ss (Ilm_ss–Psb_ss) and single-phase samples under a wide range of fO₂ (fixed with CO/CO₂ mixtures or by solid oxygen buffers) in sub-solidus conditions (1,000–1,300°C) at 1 bar. Runs lasted 24 h at 1,300°C and up to 240 h at 1,000°C and were terminated by quenching in water. All run products are polycrystalline, roughly equigranular aggregates, with grain sizes of 10–50 m. They were examined and analysed with the SEM and EMP. Tmt compositions are broadly in accordance with the current models at moderate fO₂, but significantly richer in Ti at low fO₂ and high T, due to cationic vacancies. Ilm_ss compositions depart from the predicted values practically at all fO₂ and T conditions, which is related to unsatisfactory thermodynamic models for the rhombohedral oxide. For Ilm_ss–Psb_ss assemblages the best agreement between our data and current calculations is at 1,000°C and moderately high fO₂. Otherwise, experimental and calculated data strongly disagree. The experimental data set on the three Fe–Ti oxide solid solutions presented here is intended to support new versions of both the titanomagnetite–ilmenite_ss thermo-oxybarometer and the ilmenite_ss–pseudobrookite_ss oxybarometer.     

Fe–Mg Interdiffusion in (Mg,Fe)O

We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10^?1.0 Pa to 10^?4.3 Pa, using mixed CO/CO₂ or H₂/CO₂ gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg_1-x Fe _x )_1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$ These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO.     

Low-Nitrogen Diamond Growth in the Fe–C–S System

Doklady Earth Sciences - The first results on diamond growth in the Fe–С–S system with 1 wt % S (relative to Fe) at 6 GPa and 1450°C have been reported. The diamonds obtained...     

Assemblage of Fe–Mg–Al–Ti–Zn Oxides in Granulites of the Bunger Hills,East Antarctica: Evidence of Ultrahigh-Temperature Metamorphism

Geology of Ore Deposits - The composition and interrelations of oxides (minerals of the spinel supergroup, corundum, ilmenite, rutile) and silicates (garnet, sillimanite, orthopyroxene, cordierite)...     

Fractional crystallization and the formation of thick Fe–Ti–V oxide layers in the Baima layered intrusion,SW China

The Baima layered intrusion is located in the central part of the Emeishan Large Igneous Province (ELIP). The N–S striking intrusion is ~ 24 km long and ~ 2 km thick and dips to the west. Based on variations in modal proportions and cumulus mineral assemblages, the intrusion from the base to the top is simply subdivided into a lower zone (LZ) with most of the economic magnetite layers, and an upper zone (UZ) with apatite-bearing troctolite and gabbro. The rock textures suggest crystallization of the Fe–Ti oxide slightly later than plagioclase (An_67-54) but relatively earlier than olivine (Fo_74-55), followed by clinopyroxene and finally apatite.Relatively low olivine forsterite content and abundant ilmenite exsolution lamellae in clinopyroxene indicate that the Baima parental magma is a highly evolved Fe–Ti-rich magma. Via MELTS model, it demonstrates that under a closed oxygen system, extensive silicate mineral fractionation of a picritic magma might lead to Fe and Ti enrichment and oxygen fugacity elevation in the residual magma. When such Fe–Ti-rich magma ascends to the shallower Baima intrusion, the Fe–Ti oxides may become an early liquidus phase. Well-matched olivine and plagioclase microprobe data with the results of MELTS calculation, combined with relatively low CaO content in olivine (0.02–0.08 wt.%) indicate that wall-rock contamination probably plays a weak role on oxygen fugacity elevation and the early crystallization of Fe–Ti oxides. Several reversals in whole-rock chromium and plagioclase anorthite contents illustrate that multiple recharges of such Fe–Ti-rich magma mainly occurred along the lower part of the Baima magma chamber. Frequent Fe–Ti-rich magma replenishment and gravitational sorting and settling are crucial for the development of thick Fe–Ti oxide layers at the base of the Baima layered intrusion.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Differentiation of nelsonitic magmas in the formation of the ~1.74 Ga Damiao Fe–Ti–P ore deposit, North China

The ~1.74 Ga Damiao anorthosite complex, North China, is composed of anorthosite and leuconorite with subordinate melanorite, mangerite, oxide-apatite gabbronorite, perthite noritic (i.e., jotunitic) and ferrodioritic dykes. The complex hosts abundant vein-, pod- and lens-like Fe–Ti–P ores containing variable amounts of apatite (10–60 modal%) and Fe–Ti oxides. In addition to Fe–Ti–P ores, there are also abundant Fe–Ti ores which are closely associated with Fe–Ti–P ores in the deposit. Most of Fe–Ti–P ores are dominated by Fe–Ti oxides and apatite, devoid of silicate minerals, mineralogically similar to the common nelsonites elsewhere. In contrast, Fe–Ti ores are dominated by Fe–Ti oxides with minor apatite (<5 modal %). The parental magma of these ores, estimated from olivine and apatite compositions using mineral-melt partition coefficients, has composition similar to the ferrodioritic dykes. Fe–Ti–P ores have variable Fe–Ti oxides and apatite proportions, indicating that they are cumulates. Their simple assemblage of Fe–Ti oxides and apatite and local net-texture suggest that the Fe–Ti–P ores in Damiao have formed from nelsonitic melts immiscibly separated from the ferrodioritic magma during late-stage differentiation. Fe–Ti ores are also cumulates and have mineral compositions similar to Fe–Ti–P ores. The close association between Fe–Ti and Fe–Ti–P ores indicates that the Fe–Ti ores may have also formed from the nelsonitic melts. We proposed that differentiation of nelsonitic melts accompanied by gravity settling is responsible for the formation of Fe–Ti and Fe–Ti–P ores. Such a differentiation process in nelsonitic melts is well supported by variations of Sr, Y, Th, U, REE and Eu/Eu* of apatite in Fe–Ti–P ores. Using oxides/apatite ratio of 2:1 and compositions of apatite and calculated primary oxides, we estimate the composition of the nelsonitic melt as ~52.0 wt% Fe₂O₃t, ~18.5 wt% CaO, ~14.2 wt% P₂O₅, ~8.7 wt% TiO₂, ~4.0 wt% Al₂O₃ and ~1.1 wt% MgO with minor SiO₂, K₂O, Na₂O and F. Such a nelsonitic melt is suggested to be possibly conjugated with Si-rich melts compositionally similar to the Damiao jotunitic dykes (~50 wt% SiO₂ and ~15 wt% Fe₂O₃t) which may subsequently evolve to mangeritic rocks in Damiao. Our modeling also indicates that the onset of immiscibility occurs at a time when the evolved melt has ~44 wt% SiO₂, ~21 wt% Fe₂O₃t, ~3.0 wt% TiO₂ and ~2.6 wt% P₂O₅. High oxygen fugacity and phosphorous content in magmas may play important roles in the immiscibility of nelsonitic magmas, including promoting iron enrichments and widening the two-liquid field.     

Fe–Ti–Au–U Mineralization of the Ozerninskii Ore Cluster (West Trans-Baikal Region,Russia)

Doklady Earth Sciences - Comprehensive mineralogical and geochemical studies of gold–brannerite nuggets have been carried out in alluvial deposits of Kamennyi Creek. Its source is located...     

Optical absorption of electronic Fe–Ti charge-transfer transition in natural andalusite: the thermal stability of the charge-transfer band

Differently colored natural Brazilian andalusite crystals heat-treated under reducing and oxidizing conditions were analyzed by optical spectroscopy. The intensity of a broad intense band at around 20,500 cm⁻¹ in the optical absorption spectra of all color zones of the sample is proportional to the product of Ti- and Fe-concentrations and herewith proves its attribution to electronic Fe²⁺/Ti⁴⁺ IVCT transition. The band is strictly E||c-polarized, causing an intense red coloration of the samples in this polarization. The polarization of the Fe²⁺/Ti⁴⁺ IVCT band in andalusite, E||c, shows that the electronic charge-transfer process takes place in Al–O octahedral groups that share edges with neighbors on either side, forming chains parallel to the c-axis of the andalusite structure. Under thermal treatments in air, the first noticeable change is some intensification of the band at 800°C. However, at higher temperatures its intensity decreases until it vanishes at 1,000°C in lightly colored zones and 1,100°C in darkly colored ones. Under annealing in reducing conditions at 700 and 800°C, the band also slightly increases and maintains its intensity at treatments at higher temperatures up to 1,000°C. These results demonstrate that weakening and disappearance of the Fe²⁺/Ti⁴⁺ IVCT band in spectra of andalusite under annealing in air is caused by oxidization of Fe²⁺ to Fe³⁺ in IVCT Fe²⁺/Ti⁴⁺-pairs. Some intensification of the band at 800°C is, most probably, due to thermally induced diffusion of Fe²⁺ and Ti⁴⁺ in the structure that leads to aggregation of “isolated” Ti⁴⁺ and Fe²⁺ ions into Fe²⁺–Ti⁴⁺-pairs. At higher temperatures, the competing process of Fe²⁺ → Fe³⁺ oxidation overcomes such “coupling” and the band continues to decrease. The different thermal stability of the band in lightly and darkly colored zones of the samples evidence some self-stabilization over an interaction of Fe²⁺/Ti⁴⁺-pairs involved in IVCT process.     

Origin of Fe–Ti Oxide Mineralization in the Middle Paleoproterozoic Elet’ozero Syenite–Gabbro Intrusive Complex (Northern Karelia,Russia)

Magmatic oxide mineralization widely developed in syenite–gabbro intrusive complexes is an important Fe and Ti resource. However, its origin is hotly debatable. Some researchers believe that the oxide ores were formed through precipitation of dense Ti-magnetite in an initial ferrogabbroic magma (Bai et al., 2012), whereas others consider them as a product of immiscible splitting of Fe-rich liquid during crystallization of Fe–Ti basaltic magma (Zhou et al., 2013). We consider this problem with a study of the Middle Paleoproterozoic (2086 ± 30 Ma) Elet’ozero Ti-bearing layered intrusive complex in northern Karelia (Baltic Shield). The first ore-bearing phase of the complex is mainly made up of diverse ferrogabbros, with subordinate clinopyroxenites and peridotites. Fe–Ti oxides (magnetite, Ti-magnetite, and ilmenite) usually account for 10–15 vol %, reaching 30–70% in ore varieties. The second intrusive phase is formed by alkaline and nepheline syenites. Petrographical, mineralogical, and geochemical data indicate that the first phase of the intrusion was derived from a moderately alkaline Fe–Ti basaltic melt, while the parental melt of the second phase was close in composition to alkaline trachyte. The orebodies comprise disseminated and massive ores. The disseminated Fe–Ti oxide ores make up lenses and layers conformable to general layering. Massive ores occur in subordinate amounts as layers and lenses, as well as cross-cutting veins. Elevated Nb and Ta contents in Fe–Ti oxides makes it possible to consider them complex ores. It is shown that the Fe–Ti oxide mineralization is related to the formation of a residual (Fe,Ti)-rich liquid, which lasted for the entire solidification history of the first intrusive phase. The liquid originated through multiple enrichment of Fe and Ti in the crystallization zone of the intrusion owing to the following processes: (1) precipitation of silicate minerals in the crystallization zone with a corresponding increase in the Fe and Ti contents in an interstitial melt; and (2) periodic accumulation of the residual melt in front of this zone. Unlike liquid immiscibility leading to melt splitting into two phases, this liquid dissolved the residual components of the melt. Correspondingly, such an Fe-rich liquid has unusual properties and requires further study.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

Phase relations in Fe–Ni–C system at high pressures and temperatures

We performed comparative study of phase relations in Fe_1−x Ni _x (0.10 ≤ x ≤ 0.22 atomic fraction) and Fe_0.90Ni_0.10−x C _x (0.1 ≤ x ≤ 0.5 atomic fraction) systems at pressures to 45 GPa and temperatures to 2,600 K using laser-heated diamond anvil cell and large-volume press (LVP) techniques. We show that laser heating of Fe,Ni alloys in DAC even to relatively low temperatures can lead to the contamination of the sample with the carbon coming from diamond anvils, which results in the decomposition of the alloy into iron- and nickel-rich phases. Based on the results of LVP experiments with Fe–Ni–C system (at pressures up to 20 GPa and temperatures to 2,300 K) we demonstrate decrease of carbon solubility in Fe,Ni alloy with pressure.     

Newly formed minerals of the Fe–P–S system in Kolyma fulgurite

Newly obtained data from microscopic, geochemical, and thermomagnetic studies of the large Kolyma fulgurite are presented here: the fulgurite was formed in the Holocene as a result of lightning affected black shale alluvium. The composition is very close to that of glass formed from a melt. The glass has elevated concentrations of Y, Zr, Nb, and REEs. The newly formed mineral phases have been identified: those are Al–Si glass, α-cristobalite, moissanite, native iron with a phosphorus admixture, nickel-less shreibersite (?), troilite, and possibly cohenite. The formation of these minerals is related to the melt fractionation and the effects of element concentration and segregation of ore components under conditions of the rock melting caused by the effect of high-energy plasma (lightning strike).     

Oxidation mechanisms in Al–Mg–Fe spinels. A second stage: α–Fe2O3 exsolution

A two-stage model of oxidation was devised to explain the observed variations in crystallographic parameters in two artificially oxidized natural spinels. In the first stage, oxygen is added to the crystal boundary as cations are preserved, with Fe rising in total valence and vacant sites being formed. In the second stage, oxygen is preserved and α−Fe₂O₃ intergrowth occurs, at the expense of the oxygen of the parent spinel structure. On the basis of this model, crystallochemical formulae were calculated and cations partitioned in the various conditions. It was found that, both before and after oxidation, the spinel site population varies continuously in the direction of an increase in random charge distribution, depending on the increase of heat to the crystals. This trend was found to be reversible. Cation vacancies produced during oxidation are distributed between tetrahedral site T and octahedral site M. Received: 12 June 1997 / Revised, accepted: 17 February 1998     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.     

Pb isotope variations in hydrogenetic Fe–Mn crusts from the Izu–Bonin fore-arc

Fe–Mn crusts were recovered from the western escarpment of the Bonin Ridge in the Izu–Bonin fore-arc region (dive site #824: 28.612°N, 141.803°E) at water depths of c. 2900 m using the Shinkai 6500 submersible during cruise YK 04–05. Major and trace element data and XRD mineralogy indicate that the crusts are hydrogenetic in origin. We present profiles of variations in Pb isotope composition measured in-situ by laser ablation MC-ICP-MS across two of the crusts. The isotopic variations are systematic and can be matched up between the two crusts, indicating similar growth rates. The crust Pb isotope composition rules out any local source for Pb from within the Izu–Bonin–Mariana arc system, either from hydrothermal activity or through leaching of volcanic detritus. Input of a globally well-mixed volcanic Pb component, either from aerosols or as an absorbed component on aeolian dust, has been proposed as a mechanism to explain the Pb isotope composition of Central Pacific deep water. However, the Izu–Bonin crusts are displaced to lower ²⁰⁶Pb/²⁰⁴Pb and higher ²⁰⁸Pb/²⁰⁴Pb, which requires an additional Pb source. One possibility is that as water is advected from the south, outboard of the Luzon–Ryukyu–Honshu arc system, it is progressively polluted by Pb derived by weathering and erosion of these young island arc volcanic systems. Using a constant Co-flux model, growth rates are estimated at ～ 7–13 mm/Ma, which would suggest that these crusts provide a record of changes in the composition of deep water in the Izu–Bonin fore-arc region of the western Pacific Ocean over the last 4–8 Ma. Over this interval, the main feature has been a progressive decrease in ²⁰⁷Pb/²⁰⁶Pb (0.843 to 0.839) and ²⁰⁸Pb/²⁰⁶Pb (2.088 to 2.080) with time. The interior parts have compositions similar to those of crusts from the Izu–Bonin fore-arc, while the rims have compositions similar to crusts from the central Western Pacific.     

Fe–Mg partitioning between post-perovskite and ferropericlase in the lowermost mantle

Fe–Mg partitioning between post-perovskite and ferropericlase has been studied using a laser-heated diamond anvil cell at pressures up to 154 GPa and 2,010 K which corresponds to the conditions in the lowermost mantle. The composition of the phases in the recovered samples was determined using analytical transmission electron microscopy. Our results reveal that the Fe–Mg partition coefficient between post-perovskite and ferropericlase (K _D^PPv/Fp) increases with decreasing bulk iron content. The compositional dependence of K _D^PPv/Fp on the bulk iron content explains the inconsistency in previous studies, and the effect of the bulk iron content is the most dominant factor compared to other factors, such as temperature and aluminum content. Iron prefers ferropericlase compared to post-perovskite over a wide compositional range, whereas the iron content of post-perovskite (X _Fe^PPv, the mole fraction) does not exceed a value of 0.10. The iron-rich ferropericlase phase may have significant influence on the physical properties, such as the seismic velocity and electrical conductivity at the core–mantle boundary region.     

Multistage growth of Fe–Mg–carpholite and Fe–Mg–chloritoid,from field evidence to thermodynamic modelling

We provide new insights into the prograde evolution of HP/LT metasedimentary rocks on the basis of detailed petrologic examination, element-partitioning analysis, and thermodynamic modelling of well-preserved Fe–Mg–carpholite- and Fe–Mg–chloritoid-bearing rocks from the Afyon Zone (Anatolia). We document continuous and discontinuous compositional (ferromagnesian substitution) zoning of carpholite (overall X _Mg = 0.27–0.73) and chloritoid (overall X _Mg = 0.07–0.30), as well as clear equilibrium and disequilibrium (i.e., reaction-related) textures involving carpholite and chloritoid, which consistently account for the consistent enrichment in Mg of both minerals through time, and the progressive replacement of carpholite by chloritoid. Mg/Fe distribution coefficients calculated between carpholite and chloritoid vary widely within samples (2.2–20.0). Among this range, only values of 7–11 correlate with equilibrium textures, in agreement with data from the literature. Equilibrium phase diagrams for metapelitic compositions are calculated using a newly modified thermodynamic dataset, including most recent data for carpholite, chloritoid, chlorite, and white mica, as well as further refinements for Fe–carpholite, and both chloritoid end-members, as required to reproduce accurately petrologic observations (phase relations, experimental constraints, Mg/Fe partitioning). Modelling reveals that Mg/Fe partitioning between carpholite and chloritoid is greatly sensitive to temperature and calls for a future evaluation of possible use as a thermometer. In addition, calculations show significant effective bulk composition changes during prograde metamorphism due to the fractionation of chloritoid formed at the expense of carpholite. We retrieve P–T conditions for several carpholite and chloritoid growth stages (1) during prograde stages using unfractionated, bulk-rock XRF analyses, and (2) at peak conditions using compositions fractionated for chloritoid. The P–T paths reconstructed for the Kütahya and Afyon areas shed light on contrasting temperature conditions for these areas during prograde and peak stages.