Iron Valence Research Articles

Impact of gradient zero-valent iron pollution from steel works on soil microaggregate geochemical processes and dissipative structures

Abstract: Zero-valent iron (ZVI) contamination from steel works poses significant threats to soil quality and ecosystem health, particularly affecting soil microaggregates, which are fundamental to soil structure and function. In this study, we systematically investigated the impact of gradient ZVI pollution on the organic geochemical environment of soil microaggregates around steel works located in the core water source area of the Middle Route of the South-to-North Water Diversion Project in China. Advanced analytical techniques, including X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray fluorescence spectroscopy (XRF), inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR), were employed to comprehensively characterize the geochemical processes, mineralogy, and organic matter environment of soil microaggregates. The findings revealed that soils near the steel works were acidified and strongly oxidized, with heavy metal contents, particularly Fe, significantly decreasing with increasing distance from the steel works (Fe content decreased from 27,516.2 mg/kg to 23,492.6 mg/kg). The pH of soils near the steel works was lower, while oxidation-reduction potential (ORP) and electrical conductivity were higher. XPS analysis indicated a higher content of reactive oxygen species (ROS) near the steel works and significantly lower soil organic matter content. The iron valence distribution showed spatial differences, with higher Fe2⁺ content on the surface of soil microaggregates near the steel works and Fe³⁺ dominating in areas farther away. These results suggest an evolutionary sequence of ZVI from Fe (0) oxidation to Fe(II) and then to Fe(III). The formation of dissipative structures in soil microaggregates due to ZVI contamination significantly affects soil physicochemical properties and the organic environment. This study provides valuable insights into the multifaceted impacts of industrial activities on soil ecosystems and offers a scientific basis for soil conservation and remediation strategies.

Asperomagnetism and speromagnetism in magnetic aluminosilicate glasses

In this research, we make use of mineral waste composite with elemental composition of Si, Al, Ca, Mg, K and Fe to synthesize magnetic aluminosilicate glasses (MAGlass). The produced MAGlass presented interesting magnetic and optical properties due to the presence of iron with different valence states. The elemental composition was measured by X-ray fluorescence spectroscopy. X-ray diffraction analysis confirmed the glass amorphous nature. Thermal properties such as glass transition temperature and thermal stability were analyzed by differential scanning calorimetry. The nature of the glass chemical bond structure was studied by FT-Raman analysis. UV–Vis spectroscopy studied the transmittance and absorbance in each sample, approaching the main electronic transitions, Racah parameters and gap energy. Mössbauer and magnetization measurements showed different iron valency states and interesting asperomagnetism and speromagnetism behaviors, with variations among the Fe2＋ and Fe2.5+ in the MAGlass samples.

Fate of arsenic in contaminated coastal soil induced by rising temperature and seawater intrusion

Temperature rising and seawater intrusion are expected to influence the hydrologic regime and redox conditions in coastal soil, and the fate and mechanisms of biogeochemical cycling of Arsenic (As) in the specific environment are poorly understood. This work was carried out in an anaerobic operating chamber by adding sulfate to simulate seawater intrusion under various temperature. Results demonstrated the microbial community diversity was influenced by temperature and the highest Shannon and lowest Simpson index were found at 28 °C. Firmicutes was the dominant bacteria, accounting for 81.16%–93.99%. Desulfosporosinus, with the proportion increasing with temperature, showed a significantly positive correlation with S2− for sulfate addition treatments. Actually, transformation of As was meditated by the concentration and valence of sulfur and iron in soil. The dissimilatory reduction of arsenic-bearing Fe oxides occurring in the initial stage, is suspected to be the primary driver of As release. Then, concentration of As declined in aqueous phase due to the reduction of sulfate, and the proportion of residual speciation of As in solid phase increased with temperature, ranging from 6.78% to 27.70%. The results displayed the reducing condition due to seawater intrusion and temperature change could regulate the release and sequestration of As in the coastal soil.

Synthesis, morphological characterization, and evaluation of nano zero-valent iron (nZVI) in the degradation of water contaminated with POPs

Nanostructured zero valence iron (nZVI) has been applied in advanced oxidative processes aimed at the treatment of water contaminated with Persistent Organic Pollutant (POP). Considering that such compounds cannot be eliminated by traditional treatment methods, this study proposes the synthesis of nZVI by the reduction of Iron Chloride III by sodium borohydride in the absence of O2, in ultrasound bath. The material obtained has only a wide diffraction halo at 45.13º of 2θ, with an average diameter of the crystallite calculated at 8.3 nm. The method of Brunauer, Emmett and Teller (BET method) analysis infer that the synthesized material is classified as mesoporous and showing a large surface area of 91.48 m2.g-1. According to transmission electron microscopy (TEM) the compound exhibits a core-shell type structure being the average size smaller than 50 nm. Thermogravimetric analysis demonstrates that the compound is thermally stable, exhibiting only a thermal event close to 70º C in which there is a loss of approximately 25% of mass related to water loss. The synthesis was efficient because there is no formation of metal oxides and no residue from the synthesis process according to FT-IR analyzes. To evaluate the effectiveness and present the parameters that most positively contributed to the degradation of water contaminated with 24 of the most common POPs, a chemometric study was applied considering the following variables: reaction time, concentration of applied iron nanoparticles and pH values. The approach reduces costs, time, and waste generation. Among the variables, reaction time is crucial, mainly due to solubility differences between compounds. Kinetic tests show increased efficiency after one hour, emphasizing a direct correlation between degradation rate and water solubility for the studied POPs.

Dopant site occupancies and iron valence states in SrZnxFe18−xO27 W-type hexaferrites using site-selective X-ray/electron spectroscopy

Zn-doped W-type Sr hexaferrite (SrZnxFe18−xO27; SrZnx-WHF) is an anticipated rare-earth-free hard magnetic material with strong magnetocrystalline anisotropy and saturation magnetization. To examine the origin of its high magnetic performance, the site distribution of Zn over seven crystallographically inequivalent Fe sites and the site-dependent valence states of Fe were investigated using site-selective elemental/chemical analysis techniques. The dominant occupation of Zn2+ at the 4etet(S) and 4ftet(S) tetrahedral sites was determined quantitatively using high-angular-resolution electron-channeling X-ray spectroscopy and statistical data analysis. The combined application of high-angular-resolution electron channeling electron spectroscopy and atomic-column resolution scanning transmission electron microscopy–electron energy-loss spectroscopy helped unambiguously clarify that most of the Fe2+ ions existed at the 6goct(S-S) octahedral site. Density functional theory calculations have shown that Zn doping leads to a redistribution of the charges toward Fe ions at this site. This redistribution preserves the local charge balance and amplifies the total number of parallel spins. Hence, the enhanced magnetocrystalline anisotropy and saturation magnetization in SrZnx-WHF can be inferred to originate from the charge redistribution at the 6goct(S-S) site, which is influenced by the presence of nonmagnetic Zn.

Understanding Variations in Ferrate Detection through the ABTS Method in the Presence of Electron-Rich Organic Compounds.

The chromogenic reaction between 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and ferrate [Fe(VI)] has long been utilized for Fe(VI) content measurement. However, the presence of electron-rich organic compounds has been found to significantly impact Fe(VI) detection using the ABTS method, leading to relative errors ranging from ∼88 to 100%. Reducing substances consumed ABTS•+ and resulted in underestimated Fe(VI) levels. Moreover, the oxidation of electron-rich organics containing hydroxyl groups by Fe(VI) could generate a phenoxyl radical (Ph•), promoting the transformation of Fe(VI) → Fe(V) → Fe(IV). The in situ formation of Fe(IV) can then contribute to ABTS oxidation, altering the ABTS•+:Fe(VI) stoichiometry from 1:1 to 2:1. To overcome these challenges, we introduced Mn(II) as an activator and 3,3',5,5'-tetramethylbenzidine (TMB) as a chromogenic agent for Fe(VI) detection. This Mn(II)/TMB method enables rapid completion of the chromogenic reaction within 2 s, with a low detection limit of approximately 4 nM and a wide detection range (0.01-10 μM). Importantly, the Mn(II)/TMB method exhibits superior resistance to reductive interference and effectively eliminates the impact of phenoxyl-radical-mediated intermediate valence iron transfer processes associated with electron-rich organic compounds. Furthermore, this method is resilient to particle interference and demonstrates practical applicability in authentic waters.

Mixotrophic aerobic denitrification enhanced by inorganic electron donor: Novel insights into iron valence and nirS-type denitrifying bacterial community model

Nitrogen pollution was the main factor leading to reservoir eutrophication. The removal of low-concentration nitrate pollutants in water source reservoirs is an international problem to be solved. Insufficient organic electron donors in natural reservoir are a crucial limiting factor for in situ denitrification. Microbial mixotrophic aerobic denitrification using iron as the assisted electron donor is a potential pathway to treat micropolluted water bodies. The iron/activated carbon (IAC) was used to be an assisted electron provider to advance the mixotrophic aerobic denitrification performance of denitrifying bacterial community in micro-polluted reservoir water. Upon adding IAC into the reactors, the total nitrogen (TN) reduction capacity improved >41.10 %. A slight increase in organic matter removal efficiency observed in the IAC reactors compared to the control reactors. High-throughput sequencing revealed that IAC altered the richness, and co-occurrence of denitrifying bacterial community, further advancing nitrate transformation and removal. The relative abundant of Thauera, Dechloromonas, Cupriavidus, Alicycliphilus, and Azoarcus increased and presented predominant in the IAC reactors. Meanwhile, network analysis, niche width model, neutral community model, and species abundance distribution supported this finding. The Jinpen reservoir (JP; 34°32'38" N, 107°53'53" E, located in Xi’an, North China) and Xikeng reservoir (XK; 34°32'38" N, 107°53'53" E, located in Shenzhen, South China) raw water treatment experiments demonstrated excellent TN (> 60 %) and organic matter removal efficiencies (> 44 %).

Uniformly deposition of iron phosphide quantum dots on the microscopic spongy B-C3N4 and its efficient degradation of ciprofloxacin by photo-self-Fenton process

In this research, iron phosphide quantum dots (FeP QDs) are synthesized and anchored on the microporous spongy BxCN uniformly through a novel hydrothermal-phosphorization processes. FeP@BxCN shows excellent photo-self-Fenton capability and applies to eliminate CIP from aqueous solution. Results indicate both photocatalysis and self-Fenton processes contribute to CIP degradation (photocatalysis: 69.1 %; self-Fenton: 28.2 %). The decoration of FeP QDs could effectively suppress the recombination of photogenerated carriers and improve the photocatalysis performance. They also accelerate the transformation of in situ H2O2 to •OH radicals thus enhance the efficiency of self-Fenton process. Furthermore, FeP QDs shows pretty low consumption during the self-Fenton process because of the regeneration mechanism between cationic iron species, H2O2 and anionic phosphorus. The existence of intermediate valence iron (Feɛ+) and anionic phosphorus (Pɛ-) ensured the regeneration of Fe(II) and the circulation between Fe(II), Feɛ+ and Fe(III). Optimal CIP degradation efficiency could be achieved under neutral condition and the corresponding CIP removal efficiency are 97.3 % when the initial concentration is 30 mg•L−1 and reaction within 120 min. Results propose a meaningful exploration for antibiotics degradation via photocatalytic-self-Fenton technology.

Nickel atom-clusters nanozyme for boosting ferroptosis tumor therapy

The translation of Fe-based agents for ferroptosis tumor therapy is restricted by the unstable iron valence state, the harsh catalytic environment, and the complex tumor self-protection mechanism. Herein, we developed a stable nickel-based single-atom-metal-clusters (NSAMCs) biocatalyst for efficient tumor ferroptosis therapy. NSAMCs with a nanowire-like nanostructure and hydrophilic functional groups exhibit good water-solubility, colloidal stability, negligible systemic toxicity, and target specificity. In particular, NSAMCs possess excellent peroxidase-like and glutathione oxidase-like activities through the synergistic influence between metal clusters and single atoms. The dual-enzymatic performance enables NSAMCs to synergistically promote efficient ferroptosis of cancer cells through lipid peroxidization aggregation and glutathione peroxidase 4 inactivation. Importantly, NSAMCs highlight the boost of ferroptosis tumor therapy via the synergistic effect between single-atoms and metal clusters, providing a practical and feasible paradigm for further improving the efficiency of ferroptosis tumor treatment.

Photoexcitation-induced efficient detoxification and removal of arsenite in contaminated water by a layered double hydroxide-supported polyacrylate stabilized ferrous sulfide composite

The effective detoxification and removal of arsenite (As(III)) has been widely concerned because of its strong toxicity and migration ability. In this study, we designed a layered double hydroxide-supported polyacrylate stabilized ferrous sulfide composite (PAA/FeS@LDH) and coupled it with UV excitation to purify As(III)-polluted water. The removal efficiency of As(III) under UV irradiation reached almost 100% in 120 min, and the first-order kinetic constant was 3.12 orders of magnitude higher than under dark. UV irradiation significantly accelerated the oxidation and detoxification of As(III) at the interface of PAA/FeS@LDH and treatment solution. It is attributable to the generation of reactive oxygen species (ROS) intermediates, including .O2–, .OH, and SO4.– under UV irradiation, because of the presence of the photogenerated electron-hole pairs and iron valence states cycles. Importantly, .O2– may be rapidly captured and oxidized to 1O2 on the surface of PAA/FeS@LDH that is also an important contributor to the oxidation removal of As(III). Noticeably, As(III) concentrations in the real water were rapidly reduced to below the guideline limitation of drinking water (10 μg/L) within 20 min under UV irradiation. Our outcomes provide a novel photoexcitation treatment system for the efficient detoxification and removal of As from actual wastewater.

Formation of nanophase metallic iron through charge disproportionation of ferrous iron during micrometeoroid impact‐induced splash melting

AbstractCharge disproportionation of ferrous iron has been considered as one of the mechanisms for the formation of metallic iron on the lunar surface. However, the detailed mechanism of the disproportionation reaction on the Moon is yet to be elucidated. We provide direct evidence for the ferrous disproportionation reaction that produces nano phase metallic iron (npFe0) during a rapid cooling process after splash melting from a lunar sample returned by China's Chang'e‐5 mission. Space weathering processes have resulted in the formation of three distinct zones at the rim of a pyroxene fragment, as observed through transmission electron microscopy. These zones, made up of splashed melts, newly formed melts from the substrate, and the mineral, are distinguished as I, II, and III. Quantitative analyses of the iron valence state by electron energy loss spectroscopy show that disproportionation reactions occurred in zone II at a low temperature of <570°C during a rapid cooling process. The reaction led to the production of α‐structure npFe0 and Fe3+ reserve in the glass phase. The npFe0 produced by the disproportionation reaction has a larger grain size than those formed from solar wind irradiation, implying that micrometeoroid impacts mainly contribute to the darkening of visible and near‐infrared reflectance. These findings reveal a novel rim structure by repeated space weathering and a universal formation mechanism of npFe0 during micrometeoroid impacts, suggesting that the disproportionation reaction could be widespread on airless bodies with impact‐induced splash processes.

Promoting denitrification via high electron conversion ratio in the iron valence Cycle: Prospects for Pseudomonas sp. JM-7 application in environmental engineering

The interdependence between iron and nitrogen in the environment is of utmost importance, and this study has explored the intricate relationship between denitrification and iron valence cycling using Pseudomonas sp. strain JM-7 (P. JM-7) as a model bacteria. Our research demonstrated that P. JM-7 had the ability to effectuate electron transfer from the periplasmic space to electron acceptors, such as nitrate, via Cytochrome c-proteins (c-Cyts). We found that iron valence state transformations with Fe(II)/Fe(III) promoted P. JM-7′s denitrification of nitrate coupled to yeast extract powder (YEP) oxidation. Denitrification rates depended on temperature (>21 °C) and pH (6–9). During logarithmic growth, 5 g/L YEP enabled 350 mg/L nitrate removal, increasing to 1650 mg/L in stable growth. Addition of 4 mM Fe(II)/Fe(III) increased denitrification to 500 mg/L during logarithmic growth. The dynamic test results displayed that compared to the SiO2 filler control group, iron-containing fillers could facilitate P. JM-7 to reduce 100 mg/L nitrate with 50 mg/L YEP electrons, corresponding to 6 times the maximum electron transfer efficiency in the static test. Overall, iron redox cycling significantly enhanced P. JM-7 denitrification, imparting insights into iron–nitrogen interactions. In summary, our research imparts valuable insights into the nexus between iron and nitrogen in the environment, highlighting the potential application of P. JM-7 in environmental engineering. Our findings indicate that P. JM-7 exhibits a significant denitrification capability, and further research is recommended to investigate its ability to remove phosphorus and promote sustainable environmental remediation practices.

Effect of Fe and its oxides on steam gasification mechanism of lignin using ReaxFF molecular dynamics simulations

Lignin is an important biomass component and its gasification process has been extensively studied. Iron is widely found in nature, and the corresponding iron-based catalysts have been heavily used in the study of various systems. The advantages are that it is inexpensive and not easy to pollute the environment, and it can also be extracted from the system and reused. However, studies on the effect of iron and its oxides on the steam gasification of lignin are limited, most studies have focused on supercritical water gasification. In this study, the effects of Fe and its oxides on the steam gasification process of lignin dimers were simulated using reactive force field (Reaxff) molecular dynamics (MD). By analyzing the gas products and the evolution of the structures. It was found that low valence Fe greatly improved the efficiency of lignin steam gasification, while higher valence iron oxides were significantly less effective. There were also significant differences in the distribution of gas products for different valence states of Fe. Low-valent Fe greatly improves the yield of combustible gases such as H2 and CO, while high-valent Fe is better at generating CO2. Carbon accumulation occurs on the surface of the catalyst, which reduces the catalytic effect. By comparing the effects of different temperatures on the steam gasification of lignin, it was found that increasing the temperature accelerates the decomposition process of lignin, and that the steam gasification of lignin has a critical temperature at which the yield of the main gaseous products of lignin is the highest.

Effect of different iron ratios on interaction and thermodynamic stability of bound whey protein isolate

Whey protein isolates (WPI) are known to have mineral-binding capacity to promote iron absorption. The aim of this study was to investigate the effect of iron ratio on the conformational structure of iron-bound whey protein isolate (WPI-Fe) and its thermodynamic stability. It was shown that the iron to protein ratio affects both the iron binding capacity of WPI and the iron valence state on the surface of WPI-Fe complexes. As the iron content increases, aggregation between protein molecules occurs. In addition, WPI-Fe nanoparticles have thermodynamic stability and Fe2+ has a high affinity with WPI for spontaneous exothermic reactions. This study demonstrates that WPI-Fe complexes can be used to efficiently deliver high-quality iron source (Fe2+) for future iron supplements.

Anion electrostatic insertion boosts efficient zinc ferrocyanide cathode for aqueous dual-ion battery

Prussian blue analogs (PBAs) have been considered as a kind of promising cathode materials, but its poor cycle performance severely hinders their industrialization. Herein, by combining a zinc ferrocyanide (ZnHCF) cathode with aqueous ZnSO4/LiTFSI electrolyte and zinc metal anode, we achieved a stable anion insertion-type aqueous dual-ion battery (DIB) which displays a discharge specific capacity of 75.9 mAh g–1, an energy density of 124 Wh kg–1, and a discharge plateau of 1.8 V at 5 A g–1. Its specific capacity can still reach 57.4 mAh g–1 after 1200 cycles with a Coulombic efficiency of 97 %. A reversible anion insertion mechanism of ZnHCF cathode based on the changes of the valency of iron and the insertion of TFSI– ion on crystal surface caused by electrostatic interaction is proposed and confirmed with a series of characterizations and density functional theory calculations (DFT). This work proposes the study of anion energy storage mechanism of PBAs and brings more opportunities for their large-scale applications in the future.

Tetracycline removal from aqueous solution by magnetic biochar modified with different iron valences: A comparative study

Magnetic activation is widely used to prepare highly efficient adsorbents for easy solid–liquid separation. However, knowledge on the effect of various iron valences (nZVI, Fe2SO4, FeCl3·6H2O, and K2FeO4) on the properties of magnetic biochars (Fe-BCs) and their performance is still inadequate. This study aimed to compare the properties and tetracycline (TC) removal performances of four pre-magnetic biochars derived from spent mushroom substrate (SMS) of Lentinus edodes (named as Fe0-BC, Fe2+-BC, Fe3+-BC, and Fe6+-BC). The results revealed that doping with various Fe valences formed Fe-BCs with different elemental contents, morphologies, and structures. The type of Fe valence used for doping biochars plays an important role in TC adsorption. TC adsorption capacity (qm) followed the sequence: Fe6+-BC (37.95 mg·g−1) > Fe2+-BC (31.89 mg·g−1) > Fe0-BC (25.36 mg·g−1) > Fe3+-BC (19.63 mg·g−1) > BC (11.06 mg·g−1). Fe6+-BC exhibited excellent TC adsorption capacity with the best separation performance, which was attributed to its high iron-loading and large surface area from strong corrosiveness during pyrolysis. Mechanistic analysis revealed that pore filling, π–π interactions, complexation, and hydrogen bonding mainly contribute to TC adsorption by Fe-BCs. Furthermore, Fe2+-BC showed acceptable TC adsorption capacity; thus, Fe2SO4 could be considered a promising alternative reagent to K2FeO4 in Fe-BC preparation because it is cost-effective. These results may help guide the selection of an optimal Fe source doped into BC for TC adsorption by wastewater.

Defluorination of perfluorooctanoic acid and perfluorooctane sulfonic acid by heterogeneous catalytic system of Fe-Al2O3/O3: Synergistic oxidation effects and defluorination mechanism

In this study, catalytic ozonation by Fe-Al2O3 was used to investigate the defluorination of PFOA and PFOS, assessing the effects of different experimental conditions on the defluorination efficiency of the system. The oxidation mechanism of the Fe-Al2O3/O3 system and the specific degradation and defluorination mechanisms for PFOA and PFOS were determined. Results showed that compared to the single O3 system, the defluorination rates of PFOA and PFOS increased by 2.32- and 5.92-fold using the Fe-Al2O3/O3 system under optimal experimental conditions. Mechanistic analysis indicated that in Fe-Al2O3, the variable valence iron (Fe) and functional groups containing C and O served as important reaction sites during the catalytic process. The co-existence of 1O2, OH, O2− and high-valence Fe(IV) constituted a synergistic oxidation system consisting of free radicals and non-radicals, promoting the degradation and defluorination of PFOA and PFOS. DFT theoretical calculations and the analysis of intermediate degradation products suggested that the degradation pathways of PFOA and PFOS involved Kolbe decarboxylation, desulfonation, alcoholization and intramolecular cyclization reactions. The degradation and defluorination pathways of PFOA and PFOS consisted of the stepwise removal of -CF2-, with PFOS exhibiting a higher defluorination rate than PFOA due to its susceptibility to electrophilic attack. This study provides a theoretical basis for the development of heterogeneous catalytic ozonation systems for PFOA and PFOS treatment.

Accelerated iron valence cycling in Fenton system using activated hydrogen enhanced by MIL-100(Fe) modified by nano-Pd0 Particle.

In this paper, a novel Fenton reaction system which was called MHACF-MIL-100(Fe) was constructed. In this system, based on active hydrogen-accelerated FeIII reduction, the hydroxyl radical was continuously produced with a trace amount of total iron. The MIL-100(Fe) modified with the nano-Pd0 particle could be used to activate the H2. Under normal temperature and pressure, the target organic pollutants, such as sulfamethazine and 4-chloro phenol, could be degraded fast. In the condition of initial aqueous solution pH 3, 2 g L-1 dosage of MIL-100(Fe) catalyst loaded with nano-Pd0, Pd/MIL-100(Fe), 20 mM 30 wt% hydrogen peroxide, 25 μM ferrous chloride and 60 mL H2 min-1, 97.8% of sulfamethazine and 100% 4-chloro phenol could be degraded within only 5 min, respectively. Although the surface of the catalyst exhibited more obvious defects and roughness after 5 consecutive destructive experiment cycles, its basic structure could be maintained. The removal efficiency could be maintained at least more than 79% (sulfamethazine) and 94% (4-chloro phenol). That may be mainly attributed to the degradation of hydroxyl radical.

Re-evaluating stoichiometric estimates of iron valence in magmatic clinopyroxene crystals

Clinopyroxene is a major rock forming mineral capable of incorporating diverse metal cations. As a consequence, clinopyroxene preserves valuable archives of magmatic processes. Understanding clinopyroxene is thus essential for understanding Earth’s wider chemical evolution. However, knowledge about the relative abundances of ferrous and ferric iron in magmatic clinopyroxene remains sparse because it is not currently possible to routinely measure the valence of iron in clinopyroxene crystals without either separating single crystals for bulk analysis or securing access to Mössbauer spectroscopy or a synchrotron radiation source to perform in-situ microanalysis. This is despite magmatic clinopyroxene crystals often containing appreciable quantities of ferric iron that affect its stability and behaviour in currently ill-constrained ways and limit our ability to exploit its chemistry to robustly reconstruct conditions of magma storage and evolution. Here we integrate optimised electron probe microanalysis and Mössbauer spectroscopy on endmember and single-crystal clinopyroxene samples to re-evaluate previously discredited approaches for estimating clinopyroxene ferric iron contents by stoichiometry. By ensuring that we measured all major and minor elements in clinopyroxene crystals with sufficient precision, we show that it is possible to readily obtain stoichiometric estimates of clinopyroxene ferric-to-total iron ratios with similar precisions to those derived from Mössbauer spectroscopy (1σ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\sigma }$$\\end{document}∼\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim$$\\end{document} 3.5% absolute). Being able to robustly determine clinopyroxene ferric iron contents enables us to propose a new empirical scheme for assigning clinopyroxene components that explicitly accounts for ferric iron, which is primarily hosted within esseneite component (CaFe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}AlSiO6\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{6}$$\\end{document}) in clinopyroxenes dominated by quadrilateral components and aegirine component (NaFe3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{3+}$$\\end{document}Si2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}O6\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{6}$$\\end{document}) in alkali clinopyroxenes. Our new scheme provides a framework for documenting the full spectrum of clinopyroxene compositions in both natural and experimental systems when analyses are performed with sufficient precision.

The iron oxidation state of Ryugu samples

AbstractThe Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb‐type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x‐ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross‐calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI‐type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe3+/Fetot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe3+/Fetot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so‐called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon‐rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe3+, a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe3+/Fetot > 65%) and mainly contains octahedral ferric iron. This finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.