Redox State Of Iron Research Articles

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.

Iron redox states in closed-basin lakes on early Mars: Its sensitivity to water chemistry, hydrology, and atmospheric composition

Mars has experienced drastic environmental evolution in terms of pH, redox, and desiccation. NASA’s Curiosity rover discovered that the sediments of the Pahrump Hills member of the Murray formation in Gale Crater contained different redox states of Fe oxides. To interpret the observations, understanding the factors that control iron redox states within early Gale lakes on Mars is needed. Here, we present the results of a one-dimensional geochemical model of a closed-basin lake that considers the Fe(II) photo-oxidation reaction. Depending on the source of Fe(II) (groundwater vs. river flow), lake pH, advection rate, and atmospheric composition, we defined four types of chemical profiles in the lake; namely, Fe(II) dominated, Fe(III) dominated, carbonate precipitating, and redox-stratified profiles. The Fe(III) dominated profile corresponds to the end member case in which photo-oxidation effectively oxidizes the supplied Fe(II). The redox-stratified profile, interpreted as an intermediate condition between Fe(III) dominated profile and Fe(II) dominated profile, appears in broad parameter set when Fe(II) is supplied from the groundwater, typically with a low to moderate Fe(II) input flux at acidic to alkaline pH (pH 5–9) conditions; however, the low water flux due to the nature of the groundwater may be unable to explain the measured abundance of Fe oxides in the sediments. Another endmember case, the Fe(II) dominated profile, which would also be expected to generate mixed valence Fe oxides, occurs when the pH is acidic (pH 4–5); nevertheless, the acidic pH is inconsistent with the mineral assemblages of the sediments. Carbonate precipitating profiles were limited to the case in which Fe(II) is supplied by groundwater with high Fe input flux and alkaline pH of 8–9. These results may imply either the Fe(II) input flux was high enough for the redox-stratified case or Fe(II) photo-oxidation was suppressed by turbidity or by dusty/cloudy atmosphere, or possibly that Fe(II) oxides found in the Pahrump Hills member are, at least partly, of detrital origin. Although numerous other factors (ex., effect of lake depth, variable pH throughout the lake water, detailed chemical speciation) remain unconsidered, the diverse profiles in Fe redox resulting from Fe(II) photo-oxidation reaction sheds light on interpreting the variety and the evolution of redox condition on early Mars.

The relationship between iron redox states and H2O contents in back-arc basin basaltic glasses from the North Fiji Basin

Island-arc basalts (IAB) from convergent plate margins tend to have both higher iron oxidation states (higher Fe3+/Fe2+) and higher H2O contents than the mid-ocean ridge basalts (MORB) produced by seafloor spreading, which raises the question of whether these two characteristics are causally related. Back-arc basin basalts (BABB) may help with this question, in that they are products of seafloor spreading, like MORB, but sourced from supra-subduction mantle, like IAB. Here we examine the relationship between Fe3+/Fe2+ (determined by XANES spectroscopy) and H2O contents in BABB glasses from the North Fiji Basin (NFB). The glasses cover a range of compositions from 6.1 to 8.5 wt% MgO, and from 0.16 to 1.6 wt% H2O, and have also been analysed for trace elements and Sr-Nd-Pb-isotopes. Measured Fe3+/Fe2+ range from MORB-like to slightly higher values and are positively correlated with H2O and heavy-halogen contents (Cl, Br and I). The correlation is due to lower Fe2+ rather than higher Fe3+ compared to the MORB array. This suite of BABBs is not significantly enriched in trace elements other than H2O and the heavy halogens, with MORB-like Ba/Th and other incompatible-element ratios, suggesting that the H2O and halogens may have come from dehydration of subducted lithospheric serpentinites under subsolidus conditions. Na2O is unusually variable for a suite of samples from such a limited area, and is not correlated with H2O, precluding a relationship between H2O and degree of melting. The link between H2O and low Fe2+ may be explained by H2O-rich fluids entering the transcrustal magma plumbing system, where they increase the proportion of olivine and augite to plagioclase crystallizing during the crustal evolution of the magmas. In this situation, relatively small additions of H2O can have an enhanced effect on major-element chemistry if the crustal evolution proceeds by cycles of replenish-mix-tap-crystallize (RMTX) rather than by simple fractional crystallization without repeated replenishment and tapping. The absence of any increase in Fe3+ with H2O, together with the lack of any correlation between H2O and Fe3+/Fe2+ in MORB glasses generally, suggest that various mechanisms, including more extensive olivine fractionation, were responsible for elevating Fe3+/Fe2+ in H2O-rich basalts from convergent margin settings. Proxy methods based on concentrations of elements with redox-variable partition coefficients (V, Eu) are not sensitive enough to record the subtle variations in Fe3+/Fe2+ observable by XANES spectroscopy.

Geochemical Evolution of Mg-Bentonite Affected by the Contact of Carbon Steel and a Hydrothermal Gradient

Carbon steel and bentonite are materials selected as engineered barriers for high-level radioactive waste confinement. Their long-term interaction must be evaluated to confirm the barrier’s stability. Three laboratory experiments of the carbon steel—Mg-bentonite interaction were conducted for 1, 6, and 22 months under a hydrothermal gradient. Changes in bentonite’s water content, specific surface area, and cation exchange capacity were measured. Mineralogy was studied by X-ray diffraction and scanning electron microscopy. The redistribution of aqueous species and the redox state of iron were determined across the bentonite columns. Results indicated water saturation after 22 months. The specific surface area of bentonite was reduced near contact with the steel, while the cation exchange capacity mostly decreased at 3–6 mm from the steel interface. The corrosion rate decreased with time and bentonite enriched in Fe in the first 1.5 mm from the steel contact. The formation of new Fe-bearing minerals, such as di-tri ferri-sudoite, magnetite, hematite, maghemite, lepidocrocite, siderite and ankerite was observed. Aqueous species redistributed in the porewater of bentonite with decreasing concentrations of Fe and Cl as a function of time and increasing concentrations of Na, Ca and SO4 after 22 months. This occurs under conditions where the bentonite is saturated with Mg, which conditioned the formation and nature of iron clay minerals with time.

Dissolved silica affects the bulk iron redox state and recrystallization of minerals generated by photoferrotrophy ina simulated Archean ocean.

Chemical sedimentary deposits called Banded Iron Formations (BIFs) are one of the best surviving records of ancient marine (bio)geochemistry. Many BIF precursor sediments precipitated from ferruginous, silica-rich waters prior to the Great Oxidation Event at ~2.43 Ga. Reconstructing the mineralogy of BIF precursor phases is key to understanding the coevolution of seawater chemistry and early life. Many models of BIF deposition invoke the activity of Fe(II)-oxidizing photoautotrophic bacteria as a mechanism for precipitating mixed-valence Fe(II,III) and/or fully oxidized Fe(III) minerals in the absence of molecular oxygen. Although the identity of phases produced by ancient photoferrotrophs remains debated, laboratory experiments provide a means to explore what their mineral byproducts might have been. Few studies have thoroughly characterized precipitates produced by photoferrotrophs in settings representative of Archean oceans, including investigating how residual Fe(II)aq can affect the mineralogy of expected solid phases. The concentration of dissolved silica (Si) is also an important variable to consider, as silicate species may influence the identity and reactivity of Fe(III)-bearing phases. To address these uncertainties, we cultured Rhodopseudomonas palustris TIE-1 as a photoferrotroph in synthetic Archean seawater with an initial [Fe(II)aq ] of 1 mM and [Si] spanning 0-1.5 mM. Ferrihydrite was the dominant precipitate across all Si concentrations, even with substantial Fe(II) remaining in solution. Consistent with other studies of microbial iron oxidation, no Fe-silicates were observed across the silica gradient, although Si coprecipitated with ferrihydrite via surface adsorption. More crystalline phases such as lepidocrocite and goethite were only detected at low [Si] and are likely products of Fe(II)-catalyzed ferrihydrite transformation. Finally, we observed a substantial fraction of Fe(II) in precipitates, with the proportion of Fe(II) increasing as a function of [Si]. These experimental results suggest that photoferrotrophy in a Fe(II)-buffered ocean may have exported Fe(II,III)-oxide/silica admixtures to BIF sediments, providing a more chemically diverse substrate than previously hypothesized.

Gillespite glass-ceramics

The discovery of a new glass-ceramic based on the mineral phase gillespite (BaFeSi4O10) is reported. Glasses having the stoichiometric bariumironsilicate composition were melted to obtain a range of iron redox states. Gillespite was found to precipitate only if the iron reduction ratio, [Fe+2:total Fe], in the glass was greater than 0.5. Under this condition, surface crystallization was always observed, with some large, internal gillespite crystals forming when the reduction ratio was ≥0.7. A uniform, fine-grained glass-ceramic was achieved when Pt was added as a nucleating agent. The phase assemblage typically comprised gillespite as the major phase with sanbornite (low-BaSi2O5) as a secondary phase and minor amounts of cristobalite: the gillespite crystals forming rosettes around the Pt nuclei. The relative amount of gillespite in the glass-ceramic could be increased by increasing the iron reduction ratio. Gillespite glass-ceramics have a red color which could make them useful as Cd-free red pigments.

A redox effect on the viscosity of molten pyrolite

The viscosity of molten Earth mantle has been determined for various redox states using very high temperature viscometry at 1 bar. The viscosity-temperature relationship of the most oxidised pyrolite studied here is comparable to that of a previous determination of the viscosity of a peridotite melt. For the first time, the effect of iron redox state on molten mantle viscosity has been determined by calorimetric analysis of the glass transition on extremely carefully characterised glassy samples quenched from conditions of variable fO2 using gas-mixing levitation. There is a clear trend of decreasing viscosity with increasing redox state over the range of Fe3+/ΣFe. = 0.07–0.29. We also observe an increase in glass transition temperatures with increasing melt depolymerisation (i.e., higher NBO/T ratios). Both the negative oxidation dependence of viscosity and glass transition behaviour upon depolymerisation are contradictory to the trends observed from redox viscometry of more silica-rich melts but may be consistent with the broadly diminishing positive redox viscometry trends of melts with increasing basicity.

Nitrate Reactivity in Iron (Oxy)hydroxide Systems: Effect of pH, Iron Redox State, and Phosphate

Nitrate Reactivity in Iron (Oxy)hydroxide Systems: Effect of pH, Iron Redox State, and Phosphate

The Effects of Stress on Hippocampal Neurogenesis and Behavior in the Absence of Lipocalin-2.

Lipocalin-2 (LCN2) is an acute phase protein able to bind iron when complexed with bacterial siderophores. The recent identification of a mammalian siderophore also suggested a physiological role for LCN2 in the regulation of iron levels and redox state. In the central nervous system, the deletion of LCN2 induces deficits in neural stem cells proliferation and commitment, with an impact on the hippocampal-dependent contextual fear discriminative task. Additionally, stress is a well-known regulator of cell genesis and is known to decrease adult hippocampal cell proliferation and neurogenesis. Although voluntary running, another well-known regulator of neurogenesis, is sufficient to rescue the defective hippocampal neurogenesis and behavior in LCN2-null mice by promoting stem cells' cell cycle progression and maturation, the relevance of LCN2-regulated hippocampal neurogenesis in response to stress has never been explored. Here, we show a lack of response by LCN2-null mice to the effects of chronic stress exposure at the cellular and behavioral levels. Together, these findings implicate LCN2 as a relevant mediator of neuronal plasticity and brain function in the adult mammalian brain.

A single probe for solvent dependent optical recognition of iron(II/III) and arsenite: discrimination between iron redox states with single crystal X-ray structure evidence

The detection and discrimination of Fe2+ and Fe3+ ions have been investigated using a simple probe (L), produced by the condensation of ethylenediamine and 3-ethoxysalicyaldehyde. Single crystal X-ray structures demonstrate that L interacts with Fe2+ and Fe3+. In aqueous-DMSO media, the L recognises AsO2− by fluorescence and colorimetry techniques. The AsO2− aided PET inhibition and H-bond assisted chelation enhanced fluorescence (CHEF) boost fluorescence by 91-fold. The L can detect 0.354 ppb Fe2+, 0.22 ppb Fe3+ and 0.235 ppt AsO2−.

Oxidation State and Structure of Fe in Nontronite: From Oxidizing to Reducing Conditions.

The redox reaction between natural Fe-containing clay minerals and its sorbates is a fundamental process controlling the cycles of many elements such as carbon, nutrients, redox-sensitive metals, and metalloids (e.g., Co, Mn, As, Se), and inorganic as well as organic pollutants in Earth's critical zone. While the structure of natural clay minerals under oxic conditions is well-known, less is known about their behavior under anoxic and reducing conditions, thereby impeding a full understanding of the mechanisms of clay-driven reduction and oxidation (redox) reactions especially under reducing conditions. Here we investigate the structure of a ferruginous natural clay smectite, nontronite, under different redox conditions, and compare several methods for the determination of iron redox states. Iron in nontronite was gradually reduced chemically with the citrate-bicarbonate-dithionite (CBD) method. 57Fe Mössbauer spectrometry, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) spectroscopy including its pre-edge, extended X-ray absorption fine structure (EXAFS) spectroscopy, and mediated electrochemical oxidation and reduction (MEO/MER) provided consistent Fe(II)/Fe(III) ratios. By combining X-ray diffraction (XRD) and transmission electron microscopy (TEM), we show that the long-range structure of nontronite at the highest obtained reduction degree of 44% Fe(II) is not different from that of fully oxidized nontronite except for a slight basal plane dissolution on the external surfaces. The short-range order probed by EXAFS spectroscopy suggests, however, an increasing structural disorder and Fe clustering with increasing reduction of structural Fe.

Calibration for iron redox state and oxygen fugacity in silicate glasses from x-ray absorption spectroscopy

Prior work to quantify glass Fe-redox ratios in situ using x-ray absorption spectroscopy (XAS) has relied heavily on the pre-edge region. The pre-edge-based methods do not take advantage of other information in the spectra above the pre-edge, up to and past the main edge. This study updates the previous calibration (Dyar et al., 2016a) with additional experimental glasses spanning a wide range of geologically relevant compositions (SiO2 weight % = 38.5–78.0), equilibrated over a range of oxygen fugacity (fO2) values from reducing (IW-2) to oxidizing (air), for which Fe XAS analysis has been collected for the whole spectral region (pre-edge, main edge, EXAFS). The resulting dataset was used to evaluate multiple multivariate statistical models for their ability to accurately predict log fO2 or %Fe3+. Accuracies are estimated using cross-validated root mean square error, for which purpose unseen test data are held out from the regressions. Datasets covering small compositional ranges were tested and compared with datasets covering broad compositional ranges. These ‘stratified’ sets improved predictive accuracy in some cases; however, the extra complications associated with data stratification did not justify the small improvement in accuracy. Overall, a simple partial least squares (PLS) model based on all data collected over the entire XAS region was found to result in a universal calibration for determination of log fO2 and %Fe3+ in glasses.

In Situ Reconstruction of Helical Iron Borophosphate Precatalyst toward Durable Industrial Alkaline Water Electrolysis and Selective Oxidation of Alcohols

AbstractIron‐based (pre)catalysts have attracted enormous attention for various electrooxidation reactions due to the low cost, high abundance, and multiple accessible redox states of iron. Herein, a well‐defined helical iron borophosphate (LiFeBPO) is developed as an electro(pre)catalyst for the oxygen evolution reaction (OER) and selective alcohol oxidation. When deposited on nickel foam (NF), LiFeBPO exhibits an exceptional OER performance at ambient conditions attaining a current density of 100 mA cm−2 at ≈276 mV overpotential in 1 m KOH. Notably, this anode sustains durable alkaline water electrolysis at 500 mA cm−2 for over 330 h under industrial conditions (6 m KOH and 85 °C). In –situ and ex situ investigations reveal a deep reconstruction of LiFeBPO during OER, which transforms into a 3D open porous skeleton assembled by ultrasmall, low‐crystalline α‐FeOOH nanoparticles (interfacing with NiOOH of NF). This structure contributes to exposing accessible surface active sites, as well as accelerating mass transport and bubble detachment. Moreover, this electrode also catalyzes the electrooxidation of alcohols (methanol, ethylene glycol, and glycerol) to formic acid (FA) with high selectivity and full conversion. This study provides promising solutions for designing suitable anodes for the simultaneous production of green hydrogen fuel and value–added FA from electrooxidation reactions.

FeCo2S4/Ni foam: A Bimetallic Sulfide Electrocatalyst with Efficient and Robust Behavior

The development of effective, feasible, stable, and inexpensive electrocatalysts has been a great challenge in the field of overall water splitting (WS). Herein, a bifunctional electrocatalyst (BF ECS), FeCo2S4 nanowire (FCS NWs/Ni)/nickel (Ni) foam, with superior HER/OER activity and stability was designed and fabricated using a hydrothermal method. In addition, this efficient method can be used for the synthesis of other bimetallic MCo2S4 sulfides (M = Cu, Zn, Mn, etc.). Electrochemical experiments showed the as-synthesized FCS NWs/Ni exhibited overpotentials of 350.5, 203.7, 115.97, and 62.6 mV (0.05, 0.1, 0.2, and 1 M KOH) at the current density of −10 mA cm−2 for HER, including small overpotentials of 1.51, 1.36, 1.24, and 1.11 V (10 mA cm−2) in a 0.05, 0.1, 0.2, and 1 M KOH solution for OER. The FCS NWs/Ni has a splendid electrocatalytic performance which is related to the synergistic effect of cobalt, iron, and sulfur. Specifically, it has excellent electrical conductivity, a higher specific capacity, and a rich redox state of iron, cobalt, and sulfur elements. The results demonstrate a promising method for the design and fabrication of metal BF ECS for overall water splitting.

Microbial reduction and alteration of Fe(III)-containing smectites in the presence of biochar-derived dissolved organic matter

Clay minerals are important components of solid-phase iron pools in soils, and the redox state of structurally-coordinated iron in clay minerals can significantly influence soil physicochemical properties. Due to increasing use of biochar in agriculture, the dissolved organic matter derived from biochar (BDOM) has become an unignorable fraction of dissolved organic carbon in soil systems. However, our knowledge regarding the effect of BDOM on soil biogeochemical processes (particularly on iron redox cycling) is still very limited. To examine the role of BDOM in the microbial reduction of Fe(III) in clays, BDOM was extracted from wheat straw biochar and selectively added to laboratory reactors in which lactate, Fe(III)-containing smectite (montmorillonite SWy-2 or nontronite NAu-2), and a typical iron-reducing bacterium Shewanella oneidensis strain MR-1 were used as the respective electron donor, electron acceptor, and reaction mediator. The results demonstrated that BDOM contained bio-reactive quinone moieties. BDOM amendment increased the initial rate and final extent of Fe(III) bioreduction by strain MR-1. Such promotion effect of BDOM might be ascribed to its quinone moieties functioning as electron shuttles between MR-1 cells and structural Fe(III) in smectite. Structural changes were observed in the bioreduced smectite systems, especially for NAu-2 reactors in which obvious dissolution and illitization occurred. These observations suggest that BDOM is bio-reactive and is able to stimulate the microbial reduction of Fe(III) in clay minerals, and may offer new insights into the effects of biochar application in elemental cycles in soils.

Sulfur_X: A Model of Sulfur Degassing During Magma Ascent

AbstractThe degassing of CO2 and S from arc volcanoes is fundamentally important to global climate, eruption forecasting, ore deposits, and the cycling of volatiles through subduction zones. However, all existing thermodynamic/empirical models have difficulties reproducing CO2‐H2O‐S trends observed in melt inclusions and provide widely conflicting results regarding the relationships between pressure and CO2/SO2 in the vapor. In this study, we develop an open‐source degassing model, Sulfur_X, to track the evolution of S, CO2, H2O, and redox states in melt and vapor in ascending mafic‐intermediate magma. Sulfur_X describes sulfur degassing by parameterizing experimentally derived sulfur partition coefficients for two equilibria: RxnI. FeS (m) + H2O (v) H2S (v) + FeO (m), and RxnII. CaSO4(m) SO2 (v) + O2 (v) + CaO (m), based on the sulfur speciation in the melt (m) and co‐existing vapor (v). Sulfur_X is also the first to track the evolution of fO2 and sulfur and iron redox states accurately in the system using electron balance and equilibrium calculations. Our results show that a typical H2O‐rich (4.5 wt.%) arc magma with high initial S6+/ΣS ratio (>0.5) will degas much more (∼2/3) of its initial sulfur at high pressures (>200 MPa) than H2O‐poor ocean island basalts with low initial S6+/ΣS ratio (<0.1), which will degas very little sulfur until shallow pressures (<50 MPa). The pressure‐S relationship in the melt predicted by Sulfur_X provides new insights into interpreting the CO2/ST ratio measured in high‐T volcanic gases in the run‐up to the eruption.

CYB5R3 in type II alveolar epithelial cells protects against lung fibrosis by suppressing TGF-β1 signaling.

Type II alveolar epithelial cell (AECII) redox imbalance contributes to the pathogenesis of idiopathic pulmonary fibrosis (IPF), a deadly disease with limited treatment options. Here, we show that expression of membrane-bound cytochrome B5 reductase 3 (CYB5R3), an enzyme critical for maintaining cellular redox homeostasis and soluble guanylate cyclase (sGC) heme iron redox state, is diminished in IPF AECIIs. Deficiency of CYB5R3 in AECIIs led to sustained activation of the pro-fibrotic factor TGF-β1 and increased susceptibility to lung fibrosis. We further show that CYB5R3 is a critical regulator of ERK1/2 phosphorylation and the sGC/cGMP/protein kinase G axis that modulates activation of the TGF-β1 signaling pathway. We demonstrate that sGC agonists (BAY 41-8543 and BAY 54-6544) are effective in reducing the pulmonary fibrotic outcomes of in vivo deficiency of CYB5R3 in AECIIs. Taken together, these results show that CYB5R3 in AECIIs is required to maintain resilience after lung injury and fibrosis and that therapeutic manipulation of the sGC redox state could provide a basis for treating fibrotic conditions in the lung and beyond.

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline.Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe2+, including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents.Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. These findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

High-Altitude Hypoxia Exposure Induces Iron Overload and Ferroptosis in Adipose Tissue.

High altitude (HA) has become one of the most challenging environments featuring hypobaric hypoxia, which seriously threatens public health, hence its gradual attraction of public attention over the past decade. The purpose of this study is to investigate the effect of HA hypoxia on iron levels, redox state, inflammation, and ferroptosis in adipose tissue. Here, 40 mice were randomly divided into two groups: the sea-level group and HA hypoxia group (altitude of 5000 m, treatment for 4 weeks). Total iron contents, ferrous iron contents, ROS generation, lipid peroxidation, the oxidative enzyme system, proinflammatory factor secretion, and ferroptosis-related biomarkers were examined, respectively. According to the results, HA exposure increases total iron and ferrous iron levels in both WAT and BAT. Meanwhile, ROS release, MDA, 4-HNE elevation, GSH depletion, as well as the decrease in SOD, CAT, and GSH-Px activities further evidenced a phenotype of redox imbalance in adipose tissue during HA exposure. Additionally, the secretion of inflammatory factors was also significantly enhanced in HA mice. Moreover, the remarkably changed expression of ferroptosis-related markers suggested that HA exposure increased ferroptosis sensitivity in adipose tissue. Overall, this study reveals that HA exposure is capable of inducing adipose tissue redox imbalance, inflammatory response, and ferroptosis, driven in part by changes in iron overload, which is expected to provide novel preventive targets for HA-related illness.

Iron Homeostasis in Insects.

Iron is an essential micronutrient for all types of organisms; however, iron has chemical properties that can be harmful to cells. Because iron is both necessary and potentially damaging, insects have homeostatic processes that control the redox state, quantity, and location of iron in the body. These processes include uptake of iron from the diet, intracellular and extracellular iron transport, and iron storage. Early studies of iron-binding proteins in insects suggested that insects and mammals have surprisingly different mechanisms of iron homeostasis, including different primary mechanisms for exporting iron from cells and for transporting iron from one cell to another, and subsequent studies have continued to support this view. This review summarizes current knowledge about iron homeostasis in insects, compares insect and mammalian iron homeostasis mechanisms, and calls attention to key remaining knowledge gaps.