Ferrous Iron Concentrations Research Articles

Phase conversion characteristics of lead sulfate in ferric sulfate medium

The phase transformation characteristics of lead sulfate (PbSO4) in a sulfuric acid (H2SO4) system were studied, focusing on the effects of temperature, H2SO4 concentration, ferric iron (Fe3+) concentration, sodium sulfate (Na2SO4), and potassium sulfate (K2SO4). The conversion of PbSO4 was analyzed by characterizing the composition and structure of the solid product through XRD, SEM/BSE-EDS, and FT-IR. The results indicated that the effect of temperature on PbSO4 transformation was influenced by H2SO4 concentration. The temperature threshold for PbSO4 conversion to lead jarosite (Pb-J) decreased from 150 to 90 ℃ as H2SO4 concentration decreased from 20 to 5 g/L. At 150 ℃, the amount of jarosite generated decreased significantly from 86.04 to 9.76 %. Subsequently, when H2SO4 concentration exceeded 40 g/L, PbSO4 was essentially unchanged. Concurrently, Pb-J formation correlated with the partial formation of hydronium jarosite (H-J). The production of jarosite was inhibited when the solution pH was ∼ 0.3 or lower. Furthermore, the increase in Fe3+ concentration facilitated Pb-J formation, whereas Na2SO4 and K2SO4 inhibited Pb-J formation, leading to the formation of potassium jarosite (K-J) and sodium jarosite (Na-J), respectively. This study provided insights into regulating PbSO4 conversion during sulfide ore oxygen pressure leaching.

Redox Sensitive Mineral Magnetic Signatures of Seafloor Massive Sulfide Deposits

AbstractSeafloor massive sulfide (SMS) deposits in different geological settings can have variable magnetic mineralogy, but the mechanism and implications of their spatiotemporal diversity are poorly understood. Based on seabed shallow drilling and surficial sampling of the Yuhuang hydrothermal field, Southwest Indian Ridge, we investigate here whether ubiquitous oxidative weathering affects the magnetic properties of SMS deposits. Microscopic observation and ferrous iron concentrations reveal that seafloor SMS deposits are extensively oxidized; subseafloor SMS deposits are relatively fresh, but oxidation initiates immediately after sample recovery. Negative frequency dependence of magnetic susceptibility likely due to measurement eddy currents is observed for fresh samples but not for oxidized ones, which suggests that oxidative weathering reduces the electromagnetic detectability of SMS deposits in geophysical investigations. Pyrrhotite (and probably other magnetic iron sulfide minerals), magnetite, and hematite are recognized as dominating magnetic (ferromagnetic, sensu lato) minerals in SMS deposits. Electron and quantum diamond microscope observations reveal pyrrhotite mineralization from high‐temperature reducing hydrothermal fluids, while iron‐oxides are mostly oxidation products of primary sulfides. Oxidative weathering modifies paleomagnetic records of SMS deposits. Bulk magnetic parameters vary systematically with enhanced oxidation degree. Temperature‐dependent magnetic measurements are useful tools for distinguishing the oxidation state of SMS deposits. Overall, these findings explain magnetic mineral variability in SMS deposits, linking mineral magnetic properties with seafloor geophysical investigations. Mineral magnetism can also be a redox state proxy for tracing natural and artificial environmental fluctuations in seafloor hydrothermal fields, inspiring novel interdisciplinary research to understand interactions in the dynamic Earth System.

Selenium alleviates dextran sulfate sodium-induced colitis and inhibits ferroptosis of intestinal epithelial cells via upregulating glutathione peroxidase 4.

Selenium, an essential micronutrient for humans, has been shown to be protective against ulcerative colitis (UC), but the exact mechanism remains unclear. The role of selenium, protecting against ferroptosis of intestinal epithelial cells (IECs) in colitis, was investigated in this current study. Serum selenium level and ferroptosis-related gene expression in the colonic mucosa were measured in UC patients and healthy controls. The effects of sodium selenite supplementation on experimental colitis were investigated in dextran sulfate sodium (DSS)-treated mice. The influence of sodium selenite on IEC ferroptosis was evaluated through assessing cell death rate, intracellular ferrous iron content, lipid reactive oxygen species level, and mitochondrial membrane damage of DSS-treated Caco-2 cells. Moreover, glutathione peroxidase 4 (GPX4) and acyl-CoA synthetase long-chain family member 4, ferroptosis-related genes, were detected in Caco-2 cells and mouse intestines. Serum selenium was decreased in UC patients in comparison with healthy individuals. Additionally, serum selenium level was negatively correlated with disease activity and was associated with clinical inflammation and nutrition indicators. The expression of GPX4 in the mucosa of UC was positively correlated with serum selenium level. The in vivo experiments showed that selenium treatment ameliorated DSS-induced colitis and inhibited ferroptosis in IECs. The in vitro results suggested that selenium supplementation inhibited DSS-induced ferroptosis in Caco-2 cells. GPX4 was upregulated after selenium supplementation both in vivo and in vitro. Serum selenium level was associated with IEC ferroptosis in UC patients. Selenium supplementation alleviates DSS-induced colitis and inhibits ferroptosis in IECs by upregulating the expression of GPX4.

Zinc separation from brass dust by the Fenton process

AbstractBrass polishing facilities generate waste dust rich in zinc and copper, presenting both an economic opportunity for resource recovery and an environmental challenge. The Fenton process, a promising hydrometallurgical solution, offers a way to separate zinc from this waste dust. Researchers employed an experimental design method to identify optimal parameters for zinc dissolution, including pH, ferrous iron (Fe2+) content, stirring speed, and hydrogen peroxide (H2O2) concentration. Kinetic modeling identified the optimal parameters for zinc dissolution: pH 1, 0.1 M Fe2+, 60 rpm stirring speed, 1.0% H2O2 concentration (flow rate 1 mL min−1), and a reaction time of 2 h. The kinetic data suggested a first‐order kinetic model, indicating a chemically controlled surface reaction mechanism. These findings demonstrate the Fenton process's effectiveness in zinc dissolution from brass dust. This paves the way for further research on zinc recovery methods, such as electrolysis for metallic zinc production or integration into chemical manufacturing processes.

Synthesis, evaluation, and biocompatibility study of magnetite nano particles in normal cells and cancer cells for health care application

Magnetic nanoparticles have been synthesized in a very simple and economical way by the co-precipitation method, where the effect of molar concentrations of ferric chloride anhydrous (FeCl3) and iron (II) sulphate heptahydrate (FeSO4.7 H20) on magnetite synthesis has been investigated. Also, a detailed study was conducted to study the effect of magnetite and hematite on both normal and cancerous cell lines. After this, the magnetic nanoparticles obtained were analyzed by x-ray Diffraction (XRD), scanning electron microscope (SEM) - energy dispersive x-ray (EDX), Fourier transform infrared spectroscopy (FTIR), zeta potential, vibrating sample magnetometer (VSM), atomic force microscopy (AFM), MTT test, and cell apoptotic assay. The XRD peaks for magnetite were easily discernible in the final formulation. SEM images showed round particles in nano ranges, and FTIR peaks showed the presence of magnetite. Zeta potential showed surface charges. VSM showed the magnetic property of magnetite, and AFM confirmed SEM images. It can be concluded that magnetic nanoparticles were synthesized by the co-precipitation method using an optimized molar concentration of reagents. Also, the necessity of coating uncoated magnetic nanoparticles can be seen from the MTT assay. Cell apoptotic assays have shown that synthesized magnetite nanoparticles have shown potential apoptotic activity on cancer cell lines.

The effect of iron status on gadolinium deposition in the rat brain: mechanistic implications.

Introduction: Sites associated with gadolinium (Gd) deposition in the brain (e.g., the globus pallidus) are known to contain high concentrations of ferric iron. There is considerable debate over the mechanism of Gd deposition in the brain. The role of iron transport mechanisms in Gd deposition has not been determined. Thus, we seek to identify if Gd deposition can be controlled by modifying iron exposure. Methods: Female Sprague-Dawley rats were given diets with controlled iron levels at 2-6ppm, 6ppt (20g/kg Fe carbonyl) or 48ppm for 3weeks to induce iron deficiency, overload or normalcy. They were kept on those diets while receiving a cumulative 10mmol/kg dose of gadodiamide intravenously over 2weeks, then left to washout gadodiamide for 3days or 3weeks before tissues were harvested. Gd concentrations in tissues were analyzed by ICP-MS. Results: There were no significant effect of dietary iron and total Gd concentrations in the organs, but there was a significant effect of iron status on Gd distribution in the brain. For the 3-week washout cohort, there was a non-significant trend of increasing total brain deposition and decreasing dietary iron, and about 4-fold more Gd in the olfactory bulbs of the low iron group compared to the other groups. Significant brain accumulation was observed in the low iron group total brain Gd in the 3-week washout group relative to the 3-day washout group and no accumulation was observed in other tissues. There was a strong negative correlation between femur Gd concentrations and concentrations in other organs when stratifying by dietary iron. Discussion: Gd brain deposition from linear Gd-based contrast agents (GBCAs) are dependent upon iron status, likely through variable transferrin saturation. This iron dependence appears to be associated with redistribution of peripheral deposited Gd (e.g., in the bone) into the brain.

Design and Implementation of Iron-Based Electrochemical System for Simultaneous Carbon Capture and Hydrogen Gas Recovery

The catastrophic results of climate change and energy crisis, such as the rise in wildfires, floods, and ecosystem disruptions highlight the critical need of urgent and innovative global-scale solutions for carbon dioxide (CO2) removal (CDR). Ocean-based CDR methods, leveraging the ocean's capacity as a large sink to sequester up to 30% of emissions, offer a great promise. Yet, implementing and testing marine CO2 removal (mCDR) techniques such as ocean iron fertilization (OIF) or ocean alkalinity enhancement (OAE) face significant challenges. To overcome these challenges, a novel self-operating electrochemical technology is designed and presented in this work. The proposed technology, namely electrochemical OIF (EOIF), does not only combine OIF and OAE, but also recovers hydrogen gas (H2) from seawater, offering a promising solution for achieving quantifiable and transparent large-scale mCDR. The EOIF design s focused on employing Fe/Fe-producing anodes to eliminate the production of acids at the anode in traditional electrochemical OAE systems and replace it with Fe release, where the cathode can be made from naturally abundant cost-effective materials, such as carbon. The obtained results show that the EOIF system can be implemented to increase both the concentration of ferrous iron (Fe+2) by 0-0.5 mg/L, and the seawater pH by 8% (i.e., 25% decrease in the hydrogen ions concentration). It also offers the flexibility to optimize the release of iron (Fe+2/Fe+3) by adjusting the magnitude of the electric current in the systems, as well as by optimizing the electrode material and geometry. In certain ocean regions, enhanced iron concentrations stimulate the naturally occurring biological carbon pump (BCP), leading to increased phytoplankton growth, CO2 uptake, and subsequent export of carbon to the deep ocean. Simultaneously, the system increases seawater alkalinity and the buffer capacity, enhancing CO2 solubility and storage in the shallow ocean through the solubility pump. The techno-economic assessment shows that the combined advantages of the EOIF system can lower the mCDR cost by more than 95% compared to the traditional methods. The obtained measurements demonstrate the scalability of EOIF and its ability to operate using solar energy at a lower cost. Overall, the proposed EOIF technology offers a practical, effective, and sustainable solution for addressing climate change and energy recovery on a large-scale.

Exploring the underlying mechanism by transcriptome sequencing in rats with high-voltage electrical burns and the role of iron metabolism

BackgroundClinically, the condition of skeletal muscle injury is the key to the process of high voltage electrical burn (HVEB) wound repair. The aim of this study was to identify the potential mechanisms and intervention targets of skeletal muscle injury after HVEB. MethodsA skeletal muscle injury model in SD rats with HVEB was made. Pathological examination and transcriptome sequencing of injured skeletal muscles were performed, and the expression levels of key proteins and genes in related signaling pathways were verified. ResultsSkeletal muscle injury was progressively aggravated within 48 h, then the injury was gradually repaired with scar formation occurring within 1 week. The mechanism of skeletal muscle injury is complex and varied, and ferroptosis is one of the mechanisms. The ferrous iron content in the injured skeletal muscle tissue of model rats increased significantly at 24 h after injury. After 24 h, damage to injured skeletal muscle tissue could be alleviated by increasing iron storage and blocking lysosomal phagocytosis of autophagy. ConclusionsSkeletal muscle injury caused by HVEB is characterized by adjacent endangered tissue progression after injury. Ferroptosis is involved in the mechanism of HVEB, and iron metabolism-related proteins may be potential targets for preventing progressive skeletal muscle injury.

Development of Technology for the Bioleaching of Uranium in a Solution of Bacterial Immobilization

This study presents findings regarding the kinetics of ferrous iron oxidation in solution mediated by Acidithiobacillus ferrooxidans bacteria within a continuous-flow bioreactor employing diverse types of immobilizers. The objective is to augment the rate of ferrous iron oxidation in solutions utilizing an immobilizer for Acidithiobacillus ferrooxidans strains. Immobilization represents a promising avenue for enhancing the efficiency of Fe2⁺ oxidation via acidophilic ferrooxidizing bacteria, leading to a several-fold increase in oxidation rate. A comparative analysis was conducted to evaluate the efficacy of different types of immobilizer in facilitating iron oxidation within a continuous-flow bioreactor, including the application of wood chips coated with Fe(OH)3. The results indicate that wood chips coated with iron hydroxide serve as effective type of immobilizer, facilitating the robust attachment of Acidithiobacillus ferrooxidans via electrostatic interactions between negatively charged bacteria and positively charged surfaces. Experimental investigations were conducted using novel immobilization matrices in pilot-scale tests simulating the underground borehole leaching (UBL) of uranium. The bioactivation of leaching solutions enhances the efficiency and environmental compatibility of UBL compared to conventional chemical oxidation methods. The relationships between redox potential and ferric iron content in bioactivated solutions during the UBL of uranium were delineated. The significance of this study lies in its elucidating the pivotal role of Fe2⁺ oxidation in uranium extraction processes, particularly in the context of UBL. By employing bioactivation mediated by Acidithiobacillus ferrooxidans, the study demonstrates not only enhanced uranium extraction efficiency, but also markedly improved environmental sustainability compared to traditional chemical oxidation methods. The findings reveal crucial correlations between redox potential and ferric iron concentration in bioactivated solutions.

Electrochemical ocean iron fertilization and alkalinity enhancement approach toward CO2 sequestration

Achieving net-zero emissions by 2050 requires the development of effective negative emission techniques, including ocean-based approaches for CO2 sequestration. However, the implementation and testing of marine CO2 removal (mCDR) techniques such as ocean iron fertilization (OIF) or ocean alkalinity enhancement (OAE) face significant challenges. Herein, a novel self-operating electrochemical technology is presented that not only combines OIF and OAE, but also recovers hydrogen gas (H2) from seawater, hence offering a promising solution for achieving quantifiable and transparent large-scale mCDR. Experimental results show that the electrochemical OIF (EOIF) can not only increase the concentration of ferrous iron (Fe+2) by 0–0.5 mg/L, but also significantly increases the seawater pH by 8% (i.e., a 25% decrease in the hydrogen ions concentration). The release of iron (Fe+2/Fe+3) can be regulated by adjusting the magnitude of the electric current and its form (e.g., pulsed current and polarity reversal), as well as by optimizing the electrode material and geometry. In certain ocean regions, enhanced iron concentrations stimulate the naturally occurring biological carbon pump (BCP), leading to increased phytoplankton growth, CO2 uptake, and subsequent export of carbon to the deep ocean. Simultaneously, the system increases seawater alkalinity and the buffer capacity, enhancing CO2 solubility and storage in the shallow ocean through the solubility pump. The obtained measurements demonstrate the scalability of EOIF and its ability to operate using solar energy at a lower cost. Overall, the proposed EOIF technology offers a practical, effective, and sustainable solution for addressing climate change on a large scale.

CYB561 supports the neuroendocrine phenotype in castration-resistant prostate cancer.

Castration-resistant prostate cancer (CRPC) is associated with resistance to androgen deprivation therapy, and an increase in the population of neuroendocrine (NE) differentiated cells. It is hypothesized that NE differentiated cells secrete neuropeptides that support androgen-independent tumor growth and induce aggressiveness of adjacent proliferating tumor cells through a paracrine mechanism. The cytochrome b561 (CYB561) gene, which codes for a secretory vesicle transmembrane protein, is constitutively expressed in NE cells and highly expressed in CRPC. CYB561 is involved in the α-amidation-dependent activation of neuropeptides, and contributes to regulating iron metabolism which is often dysregulated in cancer. These findings led us to hypothesize that CYB561 may be a key player in the NE differentiation process that drives the progression and maintenance of the highly aggressive NE phenotype in CRPC. In our study, we found that CYB561 expression is upregulated in metastatic and NE prostate cancer (NEPC) tumors and cell lines compared to normal prostate epithelia, and that its expression is independent of androgen regulation. Knockdown of CYB561 in androgen-deprived LNCaP cells dampened NE differentiation potential and transdifferentiation-induced increase in iron levels. In NEPC PC-3 cells, depletion of CYB561 reduced the secretion of growth-promoting factors, lowered intracellular ferrous iron concentration, and mitigated the highly aggressive nature of these cells in complementary assays for cancer hallmarks. These findings demonstrate the role of CYB561 in facilitating transdifferentiation and maintenance of NE phenotype in CRPC through its involvement in neuropeptide biosynthesis and iron metabolism pathways.

Water-saving irrigation mitigates methane emissions from paddy fields: The role of iron

Iron (Fe) and methane (CH4) emissions play crucial roles in the carbon cycling of paddy field ecosystems. However, little is known about the effect and mechanism of Fe transformation on the CH4 emission from paddy fields, especially with different water management methods. In this study, the dynamic changes in CH4 emissions and different forms of Fe and soil organic carbon content were observed in paddy fields under flooded irrigation (FI) and water-saving irrigation (WSI) (including intermittent irrigation (II) and controlled irrigation (CI)). In addition, the structural equation model was used to clarify the response relationship between CH4 emissions and Fe ions in paddy fields. The results indicate that the cumulative CH4 emissions under WSI were reduced by 29.03–61.29%. The reasons are as follows (i) WSI increased the oxidation ability of Fe to CH4 by increasing the soil ferric iron (Fe3+) content in paddy fields; (ii) WSI could reduce the substrate utilization by methanogens by transforming the Fe oxide forms to increase the binding capacity of Fe to dissolved organic carbon, which reduced the CH4 production. In addition, compared with II, CI had higher soil Fe3+ content, Fe-bound organic carbon content, and lower acetate content, so it had lower CH4 production capacity. In summary, WSI promotes the direct oxidation of CH4 by Fe3+ in paddy fields and indirectly reduces CH4 production by facilitating the combination of Fe oxides with the substrates. These findings deepen our understanding of the mechanisms of CH4 emission in paddy fields and provide new insights for research on carbon sequestration and emission reduction in paddy field ecosystems.

Salvia miltiorrhiza suppresses cardiomyocyte ferroptosis after myocardial infarction by activating Nrf2 signaling

Ethnopharmacological relevanceFerroptosis, a recently identified non-apoptotic form of cell death reliant on iron, is distinguished by an escalation in lipid reactive oxygen species (ROS) that are iron-dependent. This phenomenon has a strong correlation with irregularities in iron metabolism and lipid peroxidation. Salvia miltiorrhiza Bunge (DS), a medicinal herb frequently utilized in China, is highly esteemed for its therapeutic effectiveness in enhancing blood circulation and ameliorating blood stasis, particularly during the treatment of cardiovascular diseases (CVDs). Numerous pharmacological studies have identified that DS manifests antioxidative stress effects as well as inhibits lipid peroxidation. However, ambiguity persists regarding the potential of DS to impede ferroptosis in cardiomyocytes and subsequently improve myocardial damage post-myocardial infarction (MI). Aim of the studyThe present work focused on investigating whether DS could be used to prevent the ferroptosis of cardiomyocytes and improve post-MI myocardial damage. Materials and methodsIn vivo experiments: Through ligation of the left anterior descending coronary artery, we constructed both a wild-type (WT) and NF-E2 p45-related factor 2 knockout (Nrf2−/−) mouse model of MI. Effects of DS and ferrostatin-1 (Fer-1) on post-MI cardiomyocyte ferroptosis were examined through detecting ferroptosis and myocardial damage-related indicators as well as Nrf2 signaling-associated protein levels. In vitro experiments: Erastin was used for stimulating H9C2 cardiomyocytes to construct an in vitro ferroptosis cardiomyocyte model. Effects of DS and Fer-1 on cardiomyocyte ferroptosis were determined based on ferroptosis-related indicators and Nrf2 signaling-associated protein levels. Additionally, inhibitor and activator of Nrf2 were used for confirming the impact of Nrf2 signaling on DS's effect on cardiomyocyte ferroptosis. ResultsIn vivo: In comparison to the model group, DS suppressed ferroptosis in cardiomyocytes post-MI and ameliorated myocardial damage by inducing Nrf2 signaling-related proteins (Nrf2, xCT, GPX4), diminishing tissue ferrous iron and malondialdehyde (MDA) content. Additionally, it enhanced glutathione (GSH) levels and total superoxide dismutase (SOD) activity, effects that are aligned with those of Fer-1. Moreover, the effect of DS on alleviating cardiomyocyte ferroptosis after MI could be partly inhibited through Nrf2 knockdown. In vitro: Compared with the erastin group, DS inhibited cardiomyocyte ferroptosis by promoting the expression of Nrf2 signaling-related proteins, reducing ferrous iron, ROS, and MDA levels, but increasing GSH content and SOD activity, consistent with the effect of Fer-1. Additionally, Nrf2 inhibition increased erastin-mediated ferroptosis of cardiomyocytes through decreasing Nrf2 signaling-related protein expressions. Co-treatment with DS and Nrf2 activator failed to further enhance the anti-ferroptosis effect of DS. ConclusionMI is accompanied by cardiomyocyte ferroptosis, whose underlying mechanism is probably associated with Nrf2 signaling inhibition. DS possibly suppresses ferroptosis of cardiomyocytes and improves myocardial damage after MI through activating Nrf2 signaling.

Iron silicate perovskite and postperovskite in the deep lower mantle

Ferromagnesian silicates are the dominant constituents of the Earth's mantle, which comprise more than 80% of our planet by volume. To interpret the low shear-velocity anomalies in the lower mantle, we need to construct a reliable transformation diagram of ferromagnesian silicates over a wide pressure-temperature (P-T) range. While MgSiO3 in the perovskite structure has been extensively studied due to its dominance on Earth, phase transformations of iron silicates under the lower mantle conditions remain unresolved. In this study, we have obtained an iron silicate phase in the perovskite (Pv) structure using synthetic fayalite (Fe2SiO4) as the starting material under P-T conditions of the lower mantle. Chemical analyses revealed an unexpectedly high Fe/Si ratio of 1.72(3) for the Pv phase in coexistence with metallic iron particles, indicating incorporation of about 25 mol% Fe2O3 in the Pv phase with an approximate chemical formula (Fe2+0.75Fe3+0.25)(Fe3+0.25Si0.75)O3. We further obtained an iron silicate phase in the postperovskite (PPv) structure above 95 GPa. The calculated curves of compressional (VP) and shear velocity (VS) of iron silicate Pv and PPv as a function of pressure are nearly parallel to those of MgSiO3, respectively. To the best of our knowledge, the iron silicate Pv and PPv are the densest phases among all the reported silicates stable at P-T conditions of the lower mantle. The high ferric iron content in the silicate phase and the spin-crossover of ferric iron at the Si-site above ~55 GPa should be taken into account in order to interpret the seismic observations. Our results would provide crucial information for constraining the geophysical and geochemical models of the lower mantle.

A multi-mode Rhein-based nano-platform synergizing ferrotherapy/chemotherapy-induced immunotherapy for enhanced tumor therapy

Ferroptosis has emerged as a promising strategy for treating triple-negative breast cancer (TNBC) due to bypassing apoptosis and triggering immunogenic cell death (ICD) of tumor cells. However, the antitumor efficacy has been limited by the insufficient intracellular ferrous iron concentration required for ferroptosis and inadequate antitumor immune response. To address these limitations, we designed a multi-mode nano-platform (MP-FA@R-F NPs), which exhibited a synergistic effect of ferroptosis, apoptosis and induced immune response for enhanced antitumor therapy. MP-FA@R-F NPs target folate receptors, which are over-expressed on the tumor cell's surface to promote intracellular uptake. The cargoes, including Rhein and Fe3O4, would be released in intracellular acid, accelerating by NIR laser irradiation. The released Rhein induced apoptosis of tumor cells mediated by the caspase 3 signal pathway, while the released Fe3O4 triggered ferroptosis through the Fenton reaction and endowed the nanoplatform with magnetic resonance imaging (MRI) capabilities. In addition, ferroptosis-dying tumor cells could release damage-associated molecular patterns (DAMPs) to promote T cell activation and infiltration for immune response and induce immunogenic cell death (ICD) for tumor immunotherapy. Together, MP-FA@R-F NPs represent a potential synergistic ferro-/chemo-/immuno-therapy strategy with MRI guidance for enhanced antitumor therapy. Statement of significanceThe massive strategies of cancer therapy based on ferroptosis have been emerging in recent years, which provided new insights into designing materials for cancer therapy. However, the antitumor efficacy of ferroptosis is still unsatisfactory, mainly due to insufficient intracellular pro-ferroptotic stimuli. In the current study, we designed a multi-mode nano-platform (MP-FA@R-F NPs), which represented a potential synergistic ferro-/chemo-/immuno-therapy strategy with MRI guidance for enhanced antitumor therapy.

X‐Ray Fluorescence Determination of FeII/Fetotal Ratios in Sediments and Soils

The two most common oxidation states of iron can be determined by wavelength‐dispersive X‐ray fluorescence spectrometry relatively fast with an accuracy comparable to that of alternative methods. Main advantages for the analysis of sediments and soils are that organic matter does not interfere and solid samples can be analysed directly with minimal preparation effort. The limited availability of appropriate reference materials with certified data on their ferrous iron content turned out to be the major obstacle to implementing the method. For this reason and because no influence of the analysed geological materials on the intensity ratios of the closely adjacent Fe Kβ5 / Fe Kβ1,3 lines became evident, several rock types were selected in addition to sediments and soils to broaden and improve the calibration. Nevertheless, most reference data for calibration had to be determined by 57Fe Mössbauer spectroscopy. Plotting Fe Kβ5/Fe Kβ1,3 intensity ratios versus w FeO/w Fe2O3total ratios resulted in a correlation with R2 = 0.962 for the linear regression of all calibration data.

Denitrification dominates dissimilatory nitrate reduction across global natural ecosystems.

Denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA) are three competing processes of microbial nitrate reduction that determine the degree of ecosystem nitrogen (N) loss versus recycling. However, the global patterns and drivers of relative contributions of these N cycling processes to soil or sediment nitrate reduction remain unknown, limiting our understanding of the global N balance and management. Here, we compiled a global dataset of 1570 observations from a wide range of terrestrial and aquatic ecosystems. We found that denitrification contributed up to 66.1% of total nitrate reduction globally, being significantly greater in estuarine and coastal ecosystems. Anammox and DNRA could account for 12.7% and 21.2% of total nitrate reduction, respectively. The contribution of denitrification to nitrate reduction increased with longitude, while the contribution of anammox and DNRA decreased. The local environmental factors controlling the relative contributions of the three N cycling processes to nitrate reduction included the concentrations of soil organic carbon, ammonium, nitrate, and ferrous iron. Our results underline the dominant role of denitrification over anammox and DNRA in ecosystem nitrate transformation, which is crucial to improving the current global soil N cycle model and achieving sustainable N management.

Comparing the benthic nitrogenase activity and diazotrophic community assembly of three large river-connected freshwater lakes in eastern China

Biological nitrogen fixation (BNF) is a crucial process that provides bioavailable nitrogen and supports primary production in freshwater lake ecosystems. However, the characteristics of diazotrophic community and nitrogenase activity in freshwater lake sediments remain poorly understood. Here, we investigated the diazotrophic communities and nitrogenase activities in the sediments of three large river-connected freshwater lakes in eastern China using 15N-isotope tracing and nifH sequencing. The sediments in these lakes contained diverse nitrogenase genes that were phylogenetically grouped into Clusters I and III. The diazotrophic communities in the sediments were dominated by stochastic processes in Hongze Lake and Taihu Lake, which had heterogeneous habitats and shallower water depths, while in Poyang Lake, which had deeper water and a shorter hydraulic retention time, the assembly of the diazotrophic community in the sediments was dominated by homogeneous selection processes. Temperature and water depth were also found the key environmental factors affecting the sediment diazotrophic communities. Sediment nitrogenase activities varied in the three lakes and within distinct regions of an individual lake, ranging from 0 to 14.58 nmol/(kg·hr). Nitrogenase activity was significantly correlated with ferric iron, total phosphorus, and organic matter contents. Our results suggested that freshwater lake sediment contain high diversity of nitrogen-fixing microorganisms with potential metabolic diversity, and the community assembly patterns and nitrogenase activities varied with the lake habitat.

Investigation of the solid oxidizer effect on the metal geotechnology efficiency

Purpose. The research is aimed at increasing the useful component content in a pregnant solution during in-situ leaching (ISL) using a solid oxidizer and increasing the ferric iron concentration in the leaching solution based on laboratory research. Methods. Laboratory research is performed on a specially developed model electrolyzer for obtaining comparative data on divalent iron oxidation to trivalent iron and the change in the useful component content in a pregnant solution. Firstly, tests are conducted with a basic leaching solution, then on the oxidation of the leaching solution with a solid oxidizer in the form of a lead dioxide plate. Tests are conducted by changing sulphuric acid concentration within 5-50 g/l, amount of divalent iron ions in the solution from 0.5 up to 4.0 g, lead dioxide plate surface area from 19 to 76 cm2. The leaching time is up to 10 hours. Findings. The results of laboratory research on determining the oxidation degree of divalent iron ions and change in the oxidation-reduction potential (ORP) depending on the sulphuric acid concentration and on the initial concentration of divalent iron ions in the initial solution are presented. With a change in the sulphuric acid concentration from 5 to 50 g/l, the oxidation value of divalent iron ions increases from 26.5 to 96.5%, and with an increase in the initial solution concentration of divalent iron, the oxidation degree of divalent iron naturally decreases from 95.2 to 58.8%. In the initial leaching solution, the divalent solution concentration is 312 mg/l, and that of the trivalent solution is 288 mg/l. After oxidation with a solid oxidizer, the divalent and trivalent iron concentrations are 56 and 392 mg/l, respectively. In the course of further laboratory research using core materials from a uranium deposit, it has been revealed that when leaching with a basic solution, the uranium content in the pregnant solution is 19.36 mg/l, and when leaching with a solution after oxidation with a solid oxidizer, it is 27.9 mg/l, which is by 8.54 mg/l more. Originality. New dependences have been determined of the oxidation degree of divalent iron ions to trivalent one on the sulphuric acid concentration and on the initial concentration of divalent iron ions, as well as the useful component content in the pregnant solution on the leaching time when using a solid oxidizer. Practical implications. Using of a solid oxidizer, it is possible to increase the trivalent iron concentration in the leaching solution and the useful component content in the pregnant solution compared with the basic technology, thereby reducing the time of mining uranium reserves. Proposed technology is environmentally friendly, with low capital costs.

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.