Fetot Ratio Research Articles

Redox Properties of Structural Fe in Clay Minerals: 4. Reinterpreting Redox Curves by Accounting for Electron Transfer and Structural Rearrangement Kinetics.

Iron-bearing smectite clay minerals can act as electron sources and sinks in the environment. Previous studies using mediated electrochemical analyses to determine the reduction potential (EH) values of smectites observed that the relationship between the structural Fe2+(s)/FeTotal ratio in the smectite and EH varied based on the redox history of the smectite. We hypothesize that this behavior, referred to as redox hysteresis, results from the smectite particles not equilibrating with the applied EH over the course of the experiment (∼30 min). To test this hypothesis, we developed a model incorporating interfacial electron transfer kinetics and charge redistribution within the particle to simulate the mediated electrochemical experiments from previous studies. The simulated redox curves accurately matched the previously reported experimental redox curves of the smectite SWa-1, demonstrating that longer equilibration periods led to a decrease in redox hysteresis. We validated this experimentally by measuring the redox curve of SWa-1 after an equilibration period of at least 12 h. Furthermore, we extended the simulations to three other smectites (NAu-1, NAu-2, and SWy-2) and extracted their respective thermodynamic and kinetic parameters. This work offers a framework for interpreting and modeling redox reactions on clay surfaces, along with key parameters for four commonly studied smectites.

Ti- and Ba-rich phlogopitic micas in alkaline basic and upper mantle igneous rocks; stoichiometry, stability, and Fe valence estimation reassessed and rationalised

Ti- and Ba-rich tri-octahedral micas occur in fractionated basic igneous rocks, metasomatized mantle peridotites, metamorphosed pelites/carbonates, and hydrothermally altered mineral deposits. Electron microprobe analyses (EMP), with all iron reported as FeO, were widely used in the 1970/80s to interpret Ti and Ba substitution mechanisms, based on 22 O2– unit cell calculations, implying that cation vacancies occur in octahedral and/or intersheet sites. In 1996 EMP with chemical and physical analyses for ferric and total Fe, H2O, (OH), and element-specific Fe X-ray Absorption Spectroscopy (both K and L-edges) established valence states for Fe and Ti and cation site occupancies, that ∼50 % O replaces (OH) molecules, and that 24 anion cell formulae show the absence of cation vacancies. Cell formula calculation protocol for phlogopitic micas is refined here and results tested against the stoichiometric formula for vacancy-free phlogopite, XIIK2VIMg6IV[Si6Al2]O20(OH)4. Hypothetical sheet silicate compositions, calculated with fixed contents of vacancies linked to particular mixed-valence element substitutions, confirm that reliable unit cell formulae for natural mica solids require that each stoichiometric vacancy must be accounted for. If reliable estimates for ‘excess O’ (denoted WO2−) are assigned to EMP analyses, the proportion of the oxy-mica component in a mica solid solution can be defined. This approach is tested using published analyses for Ti- and Ba-rich biotites from fractionated basic and ultramafic volcanic igneous rocks (oxymica range 2.5–45 %; TiO2 up to 14 %; BaO up to 23 %), upper mantle peridotites (equivalent values 7–18 %; 6 %; 0.7 %), and metasomatised upper mantle (2–37 %; 9 %; 23 %). Enrichments of Ti and Ba in micas are clearly linked to the extra oxygen charge required to neutralise the more highly charged Ba2+ and Ti4+ replacing K+ and Mg2+.Substitution mechanisms involving Ba, Ti, and Fe3+ in ideal phlogopite involve coupled inter-site / inter-valence interactions so both site-ordering and valence-balance between the different cation sites must be accounted for. The cation exchange 2XIIK+ + 4VI(Mg2+ + Fe2+) + 4IVSi4+ ↔ XIIBa2+ + 3VITi4+ + 4(Altotal + Fe3+ + Crtotal)3+ is used here so that valence and site order can be considered together. Compositional variations show well-defined trends towards high-oxymica content and vacancy-free Ti and Ba mica end-members, rather than to oxy-free end-members with essential vacancies. Average compositions for different source rock micas are used to assess compositional trends; molecular WO2− values are refined by relating initial estimates directly to the wt.% TiO2 contents; and refined WO2− and stoichiometrically calculated Fe3+/Fetotal ratios ranging ∼0.1–0.5) are correlated with possible primary magmatic values.

Evolution of fluid redox in a fault zone of the Pic de Port Vieux thrust in the Pyrenees Axial Zone (Spain)

Abstract. In mountain ranges, crustal-scale faults localize multiple episodes of deformation. It is therefore common to observe current or past geothermal systems along these structures. Understanding the fluid circulation channelized in fault zones is essential to characterize the thermochemical evolution of associated hydrothermal systems. We present a study of a palaeo-system of the Pic de Port Vieux thrust fault. This fault is a second-order thrust associated with the Gavarnie thrust in the Axial Zone of the Pyrenees. The study focused on phyllosilicates which permit the constraint of the evolution of temperature and redox of fluids at the scale of the fault system. Combined X-ray absorption near-edge structure (XANES) spectroscopy and electron probe microanalysis (EPMA) on synkinematic chlorite, closely linked to microstructural observations, were performed in both the core and damage zones of the fault zone. Regardless of the microstructural position, chlorite from the damage zone contains iron and magnesium (Fetotal / (Fetotal + Mg) about 0.4), with Fe3+ accounting for about 30 % of the total iron. Chlorite in the core zone is enriched in total iron, but individual Fe3+/Fetotal ratios range from 15 % to 40 %, depending on the microstructural position of the grain. Homogeneous temperature conditions about 280–290 °C have been obtained by chlorite thermometry. A scenario is proposed for the evolution of fluid–rock interaction conditions at the scale of the fault zone. It involves the circulation of a single hydrothermal fluid with homogeneous temperature but several redox properties. A highly reducing fluid evolves due to redox reactions involving progressive dissolution of hematite, accompanied by crystallization of Fe2+-rich and Fe3+-rich chlorite in the core zone. This study shows the importance of determining the redox state of iron in chlorite to calculate their temperature of formations and to consider the fluid evolution at the scale of a fault.

WD‐XRF technique for speciation of iron and quantification of its oxidation states in geological samples using L‐series of iron X‐ray spectrum

AbstractWavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry is a fast and widely used technique for elemental analysis of geological samples from Na to U. However, it has seldom been applied for quantitative determination of oxidation states of elements in complex matrices. In this study, we present a method to determine the oxidation states of iron in geological samples by WD‐XRF. We used the FeLα1,2 fluorescence line as a tool for iron speciation and Fe(II)/Fetotal ratio determination. We found that the normalized intensity (peak height) of FeLα1,2 fluorescence line was linearly correlated with the spin multiplicity (2S + 1) of ferrous and ferric content in the samples. To account for the matrix effects of chemical environment (matrix and chemical bonding) on FeLα1,2 fluorescence line, we introduced a chemical index factor (μ) that enabled accurate determination of Fe(II)/Fetotal ratio in different types of geological samples. The method was validated using international certified reference materials and their mixtures and obtained promising results, with only 6 out of 55 determinations showing relative error more than 5% of the certified values.

X-ray absorption spectroscopic studies of Fe environments in borosilicate waste glasses synthesized under a variety of redox conditions

Fe K-edge X-ray absorption spectroscopy (XAS) was performed on two borosilicate waste glass series to determine Fe valence and coordination changes over a wide range of redox synthesis conditions. Data were also collected on eight Fe-silicate standards, including the rare phase, pellyite, that was used as a tetrahedral Fe2+O4 standard. X-ray absorption near-edge structure (XANES) linear combination fits of the Fe2+O4, Fe2+O5, and Fe3+O4 standards data to the glass spectra determined Fe2+/Fetotal ratios from 0.07 to 0.90 that are within 10 % of Mössbauer findings. As the glasses become reduced, XANES indicates Fe3+O4 tetrahedra are being replaced by Fe2+O4 tetrahedra, and possibly, Fe2+O5 sites, while extended X-ray absorption fine structure analyses show average Fe-O distances increase from 1.88 to 1.96 Å. The XANES-determined three Fe-site population distributions in the glasses are similar to findings reported in a recent molecular dynamics study of Fe redox effects in waste glass.

Effects of Lifelong Aerobic Exercise on Ferroptosis-Related Gene Expressions in Kidney of Aged Mice

PURPOSE: This study sought to explore the impact of continuous aerobic exercise throughout life on the expression of ferroptosis-related genes in aging kidneys, elucidating the role of exercise in maintaining kidney health.METHODS: Male C57BL/6 mice were divided into young control, young exercise, old control, and old exercise groups, with the latter providing access to spontaneous running wheels. Aged mice were observed until 99 weeks, while young mice were followed until 22 weeks. Kidney tissue samples underwent analysis through quantitative polymerase chain reaction, iron assays, histological staining, and pathological damage scoring.RESULTS: Expression of <i>Nphs1</i> and <i>Nphs2</i> exhibited no significant changes after exercise. However, histological analysis revealed that age-related kidney damage, including glomerular mesangial proliferation, was notably offset by lifelong aerobic exercise. The expression of <i>Slc7a11</i> and <i>Gpx4</i> remained unaffected by exercise, whereas <i>Nfe2l2</i> expression decreased significantly in the young exercise groups. <i>Acsl4</i> expression exhibited no aging- or exercise-induced differences. Additionally, <i>Tfrc</i> expression was lower in the young exercise group than in the young control group but remained consistent between the old and old-exercise groups. Total iron (Fe) increased in aged mice compared to that in the young-exercise group, and the Fe<sup>2+</sup>/Total Fe ratio was lower in the old-exercise than in the old control group.CONCLUSIONS: Lifelong aerobic exercise positively impacted kidney health by enhancing antioxidant capacity and mitigating iron accumulation. These findings underscore the significance of exercise in preventing age-related deterioration in kidney function.

Development of bioanodes rich in exoelectrogenic bacteria using iron-rich palaeomarine sediment inoculum

Microbial Fuel Cells (MFC) convert energy stored in chemicals into electrical energy thanks to exoelectrogenic microorganisms who also play a crucial role in geochemical cycles in their natural environment, including that of iron. In this study, we investigated paleomarine sediments as inoculum for bioanode development in MFCs. These sediments were formed under anoxic conditions ca. 113 million years ago and are rich in clay minerals, organic matter, and iron. The marlstone inoculum was incubated in the anolyte of an MFC using acetate as the added electron donor and ferricyanide as the electron acceptor in the catholyte. After seven weeks of incubation, the current density increased to 0.15 mA.cm−2 and a stable + 700 mV open circuit potential was reached. Community analysis revealed the presence of two exoelectrogenic bacterial genera, Geovibrio and Geobacter. Development of electroactive biofilms was correlated to bulk chemical transformations of the sediment inoculum with an increase in the Fe(II) to Fetotal ratio. Comparisons to sediments sterilized prior to inoculation confirmed that bioanode development derives from the native microbiota of these paleomarine sediments. This study illustrates the feasibility of developing exoelectrogenic biofilms from iron-rich marlstone and has implications for the role of such bacteria in broader paleoenvironmental phenomena.

Characterization of iron oxides: Valence states and naturally occurring polymorphs using chemical shift of X–ray FeLβ1 line by WD–XRF

In X–ray spectroscopic studies of 3d transition metals, Kβ1,3 lines have been extensively used for the examination of chemical states. This is because Kβ1,3 lines are the second most intense X–ray lines and are more sensitive to changes in chemical state of 3d transition metals since the valence shell 3p is involved in the transition. In order to characterize iron oxides in natural iron ores, we determined the chemical shift, asymmetric index and FWHM of the third order FeKβ1,3 lines using WD–XRF technique. Unfortunately, none of these parameters exhibited good agreement with the chemical state of iron which was desired for characterization of iron oxides. Alternatively, FeL-lines were inspected because it involves the valence shell 3d electrons and moreover Fe(II) and Fe(III) have different number of unpaired electrons in the 3d shell. Hence, FeL-lines are anticipated to represent signature of different chemical states of iron. The study established a linear relationship between chemical shift of FeLβ1 line (δβ) and spin multiplicity (2S+ 1) in iron oxide ores having both Fe(II) and Fe(III) valence states. Since (2S + 1) is an intrinsic property of valence state, the study of δβ facilitated speciation of iron. The δβ also contained potential information on structural framework of iron oxides whereby it enabled characterization of various polymorphic phases of iron oxides irrespective of their crystalline/amorphous forms and structure. The δβ was found to increase with increase in Fe(III)/Fetotal ratio in the iron oxide CRMs. Hematite (α–Fe2O3) was observed to have higher δβ than maghemite (γ–Fe2O3) which is attributed to differences in their packing structure. Magnetite (Fe3O4), on the other hand, showed an anomalous behavior due to structural resemblance with maghemite, but both were characterized successfully.

In situ simultaneous Fe K-edge XAS spectroscopy and resistivity measurements of riebeckite: Implications for anomalous electrical conductivity in subduction zones

In this paper, we address two key features of the behaviour of Fe-rich amphibole at high temperatures: (1) the Fe2+ → Fe3+ + e− exchange within the crystal bulk, and (2) the consequent rise in electrical conductivity. Cycling heating-cooling experiments were done in situ up to 542 °C (815 K) at beamline B11 of the Diamond Synchrotron Laboratory (UK). X-ray absorption spectra at the Fe K-edge and electrical resistivity were measured simultaneously on a single crystal of riebeckite with a composition very close to the ideal formula A□BNa2C(Fe2+3Fe3+2)TSi8O22W(OH)2. The Fe3+/Fetot ratio was monitored via analysis of the pre-edge feature in the XANES spectra. Our data show slight oscillations of the oxidation state of Fe with temperature cycling up to around 400 °C (673 K), followed by a substantial gradual increase in Fe2+ → Fe3+ oxidation that starts at ~450 °C (~723 K) and is completed at ~525 °C (~798 K). The conductivity (σ) measured along the crystallographic c-axis oscillates strongly with cycling temperature allowing us to conclude that it is intrinsically related to the electron hopping induced by thermal treatment. The activation-energy derived from the σ(T) trend is Ea = 74.4 ± 0.6 kJ/mol (0.77 ± 0.01 eV), in agreement with small-polaron conduction. This study provides direct and robust support of the conduction mechanisms in Fe-amphibole previously inferred from indirect methods. Given that riebeckite is a significant component in the glaucophanitic amphiboles common in blueschists associated with subducted oceanic crust, our data provide a link between atomic-scale processes and Earth-scale anomalous conductivity observed via geophysical measurements.

Experimental Constraints on the Ferric Fe Content and Oxygen Fugacity in Subducted Serpentinites

ABSTRACT Serpentinites play an important role in the delivery of water into subduction zones. In addition, serpentinites also contain ferric Fe and can transport significant redox potential. We present high-pressure and high-temperature experiments and Mössbauer spectroscopy measurements on natural lizardite and antigorite samples equilibrated at various oxygen fugacities in order to quantify the relationship between the oxygen fugacity f(O2) and the Fe3+/Fetot ratio in these two phases. In antigorite, Fe3+ partitions into the octahedral site and is charge balanced by tetrahedral Al. In lizardite, tetrahedral Fe3+ is observed only at low temperature as well as under high f(O2), whereas Fe3+ prefers the octahedral site at temperatures exceeding 500 °C and at 3 to 5 GPa. Although metastable, lizardite remains in redox equilibrium in our experiments at conditions above the lizardite to antigorite phase transformation at 300 °C and demonstrates a similar stability to antigorite. The Al concentration of lizardite is found to be temperature dependent, and it was possible to reequilibrate the Fe3+/Fetot ratio of lizardite from 0.1 to 0.9 by using redox buffers such as Fe metal, graphite, graphite–calcite, Re–ReO2 and Ru–RuO2. Our experiments on antigorite demonstrate that antigorite does not adjust its Al concentration on experimental time scales. Since Fe3+ is charge balanced by Al, it was also not possible to manipulate the Fe3+/Fetot ratio of antigorite. The coexisting phases, however, show chemical equilibration with this antigorite composition. We have retrieved the standard Gibbs energy for Fe3+- and Al-endmembers of antigorite and lizardite and calculated the metamorphic evolution of subducting serpentinites. The lizardite to antigorite transformation does not cause a decrease in the bulk Fe3+/Fetot ratio under f(O2) buffered conditions, in contrast to observations from some natural settings, but does result in the formation of additional magnetite due to antigorite having a lower Fe3+/Fetot ratio than lizardite at equilibrium. If the f(O2) of antigorite serpentinite is buffered during subduction, such as due to the presence of graphite and carbonate, the bulk Fe3+/Fetot ratio decreases progressively. On the other hand, in a closed system where the bulk serpentinite Fe3+/Fetot ratio remains constant, the f(O2) increases during subduction. In this scenario, the f(O2) of an antigorite serpentinite with a typical Fe3+/Fetot ratio of 0.4 increases from the fayalite–magnetite–quartz to the hematite–magnetite f(O2) buffer during dehydration. These f(O2) results confirm earlier inferences that fluids produced by antigorite dehydration may not contain sufficient oxidised sulphur species to oxidise the mantle wedge. Sufficiently high levels of f(O2) to mobilise oxidised sulphur species may be reached upon antigorite dehydration, however, if closed system behaviour maintains a high bulk redox potential across the lizardite to antigorite phase transformation. Alternatively, oxidation of the mantle wedge might be achieved by oxidising agents from sources in subducted oceanic crust and sediments.

Iron oxidation state in serpentines and magnesian chlorites of subduction-related rocks

Abstract. The ferric iron content in hydrothermally altered ultrabasic rocks and their major minerals, serpentines and Mg-chlorites, is important for establishing the oxidation state budget from oceanic ridges to subduction zones, in carbonaceous chondrites, and for modeling phase equilibria. A compilation of literature Mössbauer spectroscopic data on serpentines and magnesian chlorites from high-pressure ophiolites yields much lower ferric-to-total-iron ratios (Fe3+ / Fetotal) than those obtained on similar samples by X-ray absorption near-edge spectroscopy (XANES), leading to contradictory estimates of the ferric iron budget of subduction zones. New Mössbauer analysis of antigorite and Mg-chlorite samples from suites of high-pressure ophiolitic terrains of various Phanerozoic ages confirms the low and homogeneous values previously obtained by this technique, while lizardite inherited from oceanic hydrothermal alteration is ferric iron rich. We argue that XANES values may be biased by photo-oxidation when samples have a high Mg content, which is the case for serpentines and chlorites from subduction zones. Photo-oxidation is less important in Fe-poor phyllosilicates of the mica and talc families and does not affect the Fe-rich serpentines (greenalite, cronstedtite) of meteorites or Fe-rich terrestrial phyllosilicates. Mössbauer Fe3+ / Fetotal ratios of serpentine confirm the occurrence of a major redox change at the lizardite–antigorite transition near 300–400 ∘C rather than at the dehydration of antigorite at 500–650 ∘C in serpentinites from high-pressure ophiolites.

Preservation of mantle heterogeneities and serpentinization signature during antigorite dehydration: The example of the Bergell contact aureole

AbstractMajor, minor, and trace element geochemistry as well as iron oxidation state and isotopes were investigated in serpentinites and olivine‐talc fels present along a metamorphic gradient in the Bergell contact aureole (Central European Alps) to evaluate element mobility during serpentine. This aureole is an ideal target to study dehydration of mantle rocks due to the increase in temperature from greenschist facies conditions (350°C) to amphibolite facies conditions (750°C) at low pressures of 0.4 GPa. Petrography and geochemistry document several events of fluid–rock interaction and metamorphism. Serpentinization of the mantle rocks started on the ocean floor. Subsequent Alpine regional metamorphism led to the formation of antigorite‐serpentinites containing olivine and diopside. These antigorite‐serpentinites were transformed into olivine‐talc fels in a large part of the contact‐aureole. Bulk‐rock major and trace element compositions maintain the geochemical signature of the precursor antigorite‐serpentinites. No apparent changes are indeed observed despite the fact that major dehydration reactions occurred. In addition, changes neither in Fe3+/Fetot ratio nor in δ56Fe values were observed. Local composition variations of antigorite‐serpentinites and olivine‐talc fels reflect chemical heterogeneities related to protolith composition and serpentinization processes on the ocean floor prior to contact metamorphism. Hence, prograde dehydration reactions occurring during contact metamorphism did not induce substantial element mobility, change in redox state, or isotopic fractionation in these contact metamorphic rocks.

Feiite: Synthesis, stability, and implications for its formation conditions in nature

Abstract Feiite (Fe3TiO5) is a high-pressure Fe-Ti oxide mineral recently discovered in martian meteorite Shergotty. Feiite is isostructural with Fe4O5, a high-pressure iron oxide stable at pressures >10 GPa. The stability of feiite has yet to be studied, as it has not previously been synthesized in the laboratory. To determine the minimum pressure at which feiite can be synthesized, we have conducted multi-anvil experiments at 1200 °C and at pressures ranging from 7 to 12 GPa. Major element compositions and XRD patterns indicate that we successfully synthesized feiite with an orthorhombic unit cell (Cmcm structure) in experiments conducted at pressures 8 GPa or greater. Relative to A2B2O5 phases with similar structure, feiite can be synthesized at lower pressures. The coexistence of feiite and liuite (FeTiO3-perovskite) in Shergotty indicates that the upper pressure limit of feiite stability is above 15 GPa. To investigate the effect of oxygen fugacity on the composition and stability of feiite, we conducted an additional series of experiments at 1200 °C and 10 GPa pressure in which we varied the Fe3+/Fetotal ratio of the experimental starting materials. In doing so, we identified a minimum Fe3+ content necessary to stabilize the feiite structure (Fe3+/Fetotal = 0.26 at 10 GPa and 1200 °C). The importance of Fe3+ for feiite stability suggests this phase would not form in lunar or HED meteorites, where iron-titanium oxides contain little to no ferric iron. Though our experimental results can only place a lower limit on the shock pressures experienced in Shergotty, the determined pressure stability indicates feiite could also be present in diamond-bearing terrestrial rocks sourced from the upper mantle or transition zone. Additionally, the presence of feiite would be an indicator of source Fe3+/Fetotal.

C-O-H-S fluids released by oceanic serpentinite in subduction zones: Implications for arc-magma oxidation

Subducted oceanic serpentinite carries H2O, ferric iron, carbon and sulfur into the subduction zone, where they are stepwise released during dehydration. These C-O-H-S fluids are intimately linked to magma oxidation and ore formation within magmatic arcs. However, the mechanism of transfer of carbon, sulfur and ferric iron into fluids is poorly known. It is also controversial whether the C-O-H-S fluids can oxidize arc magmas. We present new thermodynamic models for serpentinite to predict the species produced in C-O-H-S fluids during subduction. Closed system modeling provides molar concentrations of species at different P-T conditions, and shows that reducing species generally have high solubilities at low P-T conditions. Oxidizing species mainly partition into the fluid at higher P-T conditions. The concentration of iron in fluids is much lower than that of other major elements. Open-system fluid fractionation shows that only 5-14% of the carbon is lost to the mantle wedge, while the loss of sulfur is as high as 55-100% at sub-arc depths. Almost all carbon and sulfur lost are released as oxidizing species. The redox properties of the fluids are controlled by sulfur, resulting in an oxygen fugacity of the fluids that is 0.6-0.95 log units higher than the HM buffer. Sulfur loss is a function of the whole-rock composition (e.g., Mg/Si, Al, Ca, and especially Fe3+/Fetot ratio) and the geothermal gradient of the subduction zone, with elevated sulfur fluxes predicted for serpentinite in cold subduction zones. The maximum amount of sulfur released in a cold subduction regime is 5.5 times higher than in a warm subduction regime. Our modeling results are consistent with petrological observations and global-arc-basalt oxygen fugacity calculations and highlight that the C-O-H-S fluids released from the subducted slab may contribute considerably to the composition of arc magmas.

Electrical Transport in Iron Phosphate-Based Glass-(Ceramics): Insights into the Role of B2O3 and HfO2 from Model-Free Scaling Procedures.

In this work, we report the effect of the addition of modifiers and network formers on the polaronic transport in iron phosphate glasses (IPG) in two systems of HfO2–B2O3–Fe2O3–P2O5, to which up to 8 mol% boron and hafnium are added. The addition of oxides significantly changes the Fe2+/Fetotal ratio, thus directly affecting the polaron number density and consequently controlling DC conductivity trends for both series studied by impedance spectroscopy. Moreover, we found that short-range polaron dynamics are also under the influence of structural changes. Therefore, we have studied them in detail using model-free scaling procedures, Summerfield and Sidebottom scaling. An attempt to construct a super-master curve revealed that in addition to change in polaron number density, also the polaron hopping lengths change, and Sidebottom scaling yields a super-master curve. The spatial extent of the localized motion of polarons is correlated with polaron number density and two distinct regions are observed. A strong increase in the spatial extent of the polaron hopping jump could be related either to the structural changes due to the addition of HfO2 and B2O3 and their effects on the formation of polarons or to an inherent property of polaron transport in IP glasses with low polaron number density.

Structural, redox and isotopic behaviors of iron in geological silicate glasses: A NRIXS study of Lamb-Mössbauer factors and force constants

We report a combined conventional Mössbauer and synchrotron Nuclear Resonant Inelastic X-ray Scattering (NRIXS) study of a series of basalt, andesite, dacite, and rhyolite glasses at temperatures ranging from 5 to 1223 K. These glasses were synthesized under controlled oxygen fugacities and span a wide range of Fe3+/Fetot ratios. As expected from theory, we find that in these glasses, the inverse of the Lamb-Mössbauer factor (the recoil-free fraction) correlates linearly with the fraction of the conventional Mössbauer spectrum that can be ascribed to Fe3+. Extrapolating the linear relationships to pure Fe3+ and Fe2+ endmembers yields a ratio for the Lamb-Mössbauer factors C of Fe3+ and Fe2+ of 1.203 ± 0.017 (1σ), with no clear dependence on the chemical composition of the glass. We show that the materials studied follow the harmonic approximation up to 1223 K for olivine and 773 K for basaltic glass, allowing us to extrapolate C in temperature. The temperature-dependence of C is well approximated by the formula C=1.203±0.033T/300 over the temperature range 50–750 K. This calibration is used to correct previous redox ratio determinations. We investigate how chemical composition and iron redox state influence the mean force constant of iron in glasses, a key driver of Fe isotopic fractionation during magma generation and differentiation. As previously documented by Dauphas et al. (2014), we find clear correlation between bond strength and iron redox ratio that is secondarily modulated by coordination effects in more alkali-rich felsic magmas. New data on simplified glass compositions reveal that network modifiers, notably K and Na, seem to exert an important control on Fe2+ bond strengths. The refined ratio of Mössbauer factors for Fe2+ and Fe3+ is used to improve on calibrations of iron redox state in geological glasses using XANES spectroscopy. We reevaluate the Fe3+/Fetot ratio of MORBs based on previously published XANES and Mössbauer data. 0.087±0.005

Successive phases of serpentinization and carbonation recorded in the Sivas ophiolite (Turkey), from oceanic crust accretion to post-obduction alteration

The ophiolite of Sivas (Turkey) was studied in order to define the chronology of different alteration events related to a series of serpentinization and carbonation episodes. Six samples were investigated, representative of different types of ophicalcite (partially carbonated serpentinite). X-ray diffraction (XRD) and Mössbauer spectroscopy were used to determine the bulk mineralogy and the bulk Fe3+/Fetot ratio, respectively. Electron microprobe and secondary ion mass spectrometer (SIMS) analyses were also conducted to identify the chemical composition of different mineral phases in addition to the carbon and oxygen isotopic compositions of calcite. An initial, i.e. pre-obduction, phase of olivine and pyroxene serpentinization was followed by a brecciation event associated with precipitation of massive serpentine. This first alteration event occurred during exhumation of the peridotites to the seafloor, followed by a carbonation event at temperatures in the range 35‒100 °C. A low-temperature (∼35 °C) carbonation event occurred between 90 and 65 Ma. Finally, a reheating of the system likely occurred after the obduction at 55‒40 Ma, resulting in a carbonation episode followed by late serpentinization. Our study presents the first direct evidence of serpentinization after obduction. In that geological context, the hydrogen produced during the proposed multiphase serpentinization may have been trapped by the salt deposits overlying the ophiolite but subsurface data will be necessary to define potential traps and reservoirs; further studies are also needed to determine whether the serpentinization process is still ongoing.

Rate limitations of nano-scale weathering front advance in the slow-eroding Sri Lankan Highlands

In the Sri Lankan Highlands denudation and chemical weathering represent the low-end member in global weathering rates. Here we report on the causes for these low rates in corestones from a highly weathered saprolite profile. By using electron microprobe and transmission electron microscopy (TEM) analyses, we investigated weathering reactions, and derived rates of pyroxene and biotite oxidation. High-resolution TEM analyses on primary minerals showed that the initial weathering products are non-crystalline and that these form the precursors of secondary minerals (kaolinite and smectite). The dissolution of primary minerals is characterised by sharp reaction fronts in the absence of chemical gradients, hence, dissolution can best be described by a dissolution – reprecipitation process. The first observable weathering reaction is the oxidation of structural Fe(II) in pyroxene and biotite. This oxidation is restricted to distinct zones within the minerals without the formation of oxidized layers. While the oxidation is not accompanied by chemical changes, the oxidation of structural Fe(II) in biotite may cause lattice distortion. Pyroxene and biotite oxidation rates were calculated at the corestone-scale by using the gradient of bulk rock Fe(II)/Fetotal ratios, assuming that oxidation is coupled to the weathering front advance rate. At the mineral-scale, oxidation rates were calculated by using gradients of in situ Fe(II)/Fe(III) ratios measured with electron energy-loss spectroscopy (EELS) within the minerals assuming a coupled oxidation-cation diffusion process. The mineral-scale oxidation rates are significantly higher, log Ominin situ = −11 molmin m−2 s−1, than corestone-scale oxidation rates, log Omin = −13 to −15 mol m−2 s−1. We explain the difference to result from the fact that corestone-scale rates average the oxidation over the entire mineral surface. Because at the corestone-scale pyroxene oxidation rates are also similar to dissolution rates, we infer that oxidation preconditions Fe(II)- bearing primary silicate minerals to weathering. However, although oxidation is initiating chemical weathering in this setting and is limited by the supply of O2, overall conversion of bedrock to saprolite is driven by the formation of porosity by fracture formation during this reaction, which allows for fluid transport and subsequent plagioclase weathering. We conclude that in compact bedrock nm- to µm-scale fracture- and porosity generation are the processes that drive weathering in tectonically quiescent regions. They are also the processes at depth that couple the weathering zone with processes at its surface. Finally, the formation of secondary surface layers at the nm-scale is essential in controlling the equilibrium in the local weathering environment and hence mineral dissolution. These layers are likely also those that control isotope fractionation in the weathering zone.

Geochemistry of iron and sulfur in the Holocene marine sediments under contrasting depositional settings, with caveats for applications of paleoredox proxies

Cycling and fates of iron (Fe) and sulfur (S) in marine sediments are influenced by depositional settings to differential extents. The information is crucial for addressing the responses of their benthic diagenesis to changing climates and environments and also for reconstructing paleo-depositional conditions, but has not been well constrained. Detailed chemical speciation was utilized to characterize geochemistry of Fe and S, and then to reveal the impacts of depositional settings on their diagenesis at three locations, representing contrasting depositional environments: (i) highly dynamic Yangtze River estuary (YRE), (ii) the depocenter of South Yellow Sea (SYS), which is only remotely impacted by large river, and (iii) the middle Okinawa trough (OT), a back-arc deep basin along the outer edge of the East China Sea (ECS) slope. Results show that the YRE sediments favor accumulation of total highly reactive Fe (FeHR), while the SYS sediments are poor in FeHR due to low FeHR in their source material and/or preferential trapping of FeHR during sediment transport through the semi-enclosed Bohai Sea. Ferruginous sediment regimes in the highly dynamic YRE system facilitate Fe(III) reduction and burial of unsulfidized Fe(II), while the SYS and OT sediments favor sulfate reduction and pyritization of Fe(II). Pyrite is always the main sink of reduced S that escapes reoxidation in the entire continental margin, regardless of depositional environments. Abundant reactive Fe(III) but low total reduced inorganic sulfide (TRIS) contents in the three sites suggest that TRIS burial is largely controlled by the availability of degradable OC and/or dynamic regimes of sediments. The applicability of two widely used Fe- and S-based proxies to distinguish bottom-water conditions, that is, OC/TRIS ratio and FeHR to total Fe (FeHR/FeT) ratio, were examined in the three contrasting environments, and caveats were given for future applications of the two proxies.

A new high-pressure experimental apparatus to study magmatic processes at precisely controlled redox conditions

Abstract Oxygen fugacity (fO2) is typically controlled in high P-T experiments by using solid-state redox buffer assemblages. However, these are restricted to impose discrete fO2 values, often with significant gaps between neighboring assemblages. Semi-permeable hydrogen membranes (Shaw 1963) are often used in internally heated pressure vessels for more flexible fO2 control in hydrous experiments; however, their implementation in more widely available externally heated pressure vessels has not yet gained space. We propose a prototype molybdenum-hafnium carbide (MHC) pressure vessel apparatus that simultaneously allows rapid quenching and flexible, precise, and accurate redox control via a custom-designed hydrogen membrane. Test runs with two membranes at a time, one imposing and another one monitoring fH2, demonstrated that 95% of the imposed hydrogen pressure was attained inside the pressure vessel within 2 h at 800–1000 °C, after which a steady state equilibrium was established. Furthermore, experiments comparing redox-dependent Cu solubility in silicate melts at fO2 imposed by the fayalite-magnetite-quartz, Re-ReO2, and MnO-Mn2O3 buffers and identical target fO2 imposed by the hydrogen membrane confirmed consistency between the two methods within 0.25 log units fO2 deviation at T = 900 °C and P = 2000 bar. This powerful yet cost-effective and low-maintenance apparatus may open up new pathways for studying redox reactions in hydrous magmas and magmatic fluids. As a proof of concept, we conducted near-liquidus phase-equilibrium experiments with H2O-saturated calc-alkaline basalt and shoshonite melt compositions at five different fO2 values equally distributed between half log unit below the Ni-NiO buffer (NNO-0.5) and NNO+2.7. Most experiments crystallized olivine, clinopyroxene, and Ti-magnetite. The Mg# of the olivine increased with fO2, and the Fe3+/Fetotal ratios in the silicate melt were determined based on Fe(II)-Mg exchange between olivine and melt. The Fe3+/Fetotal ratios in the shoshonite melt were systematically higher by about 0.06 ± 0.01 than those in the calc alkaline basalt melt at identical fO2. The values determined for the basaltic melt were consistent within 1σ error (<0.033 deviation) from those predicted by the equation of Kress and Carmichael (1991). The Fe-Ti exchange coefficient between magnetite and silicate melt increases from 1.73 ± 0.19 (1σ) at NNO –0.5 to +7.12 ± 0.36 at NNO+2.7 for shoshonite and has a similar range for the calc-alkaline basalt.