Fe Oxides Research Articles

First Insight into the Mobilization and Sequestration of Arsenic in a Karstic Soil during Redox Changes.

Karst terrains provide drinking water for about 25% of the people on our planet, particularly in the southwest of China. Pollutants such as arsenic (As) in the soil can infiltrate groundwater through sinkholes and bedrock fractures in karst terrains. Despite this, the underlying mechanisms responsible for As release from karst soils under redox changes remain largely unexplored. Here, we used multiple synchrotron-based spectroscopic analyses to explore As mobilization and sequestration in As-polluted karstic soil under biogeochemical conditions that mimic field-validated redox conditions. We observed that As in the soil exists primarily as As(V), which is mainly associated with Fe(oxyhydr)oxides. The concentration of the dissolved As was high (294 μM) and As(III) was dominant (∼95%) at low Eh (≤-100 mV), indicating the high risk of As leaching under reducing conditions. This As mobilization was attributed to the fact that the dissolution of ferrihydrite and calcite promoted the release and reduction of associated As(V). The concentration of the dissolved As was low (17.0 μM) and As(V) was dominant (∼68%) at high Eh (≥+100 mV), which might be due to the oxidation and/or sequestration of As(III) by the recrystallized ferric phase. Our results showed that the combined effects of the reductive release of As(V) from both ferric and nonferric phases, along with the recrystallization of the ferric phase, govern the redox-induced mobilization and potential leaching of As in soils within karst environments.

Biochar and Straw Amendments over a Decade Divergently Alter Soil Organic Carbon Accumulation Pathways

Exogenous organic carbon (C) inputs and their subsequent microbial and mineral transformation affect the accumulation process of soil organic C (SOC) pool. Nevertheless, knowledge gaps exist on how different long-term forms of crop straw incorporation (direct straw return or pyrolyzed to biochar) modifies SOC composition and stabilization. This study investigated, in a 13-year long-term field experiment, the functional fractions and composition of SOC and the protection of organic C by iron (Fe) oxide minerals in soils amended with straw or biochar. Under the equal C input, SOC accumulation was enhanced with both direct straw return (by 43%) and biochar incorporation (by 85%) compared to non-amended conventional fertilization, but by different pathways. Biochar had greater efficiency in increasing SOC through stable exogenous C inputs and inhibition of soil respiration. Moreover, biochar-amended soils contained 5.0-fold greater SOCs in particulate organic matter (POM) and 1.2-fold more in mineral-associated organic matter (MAOM) relative to conventionally fertilized soils. Comparatively, although the magnitude of the effect was smaller, straw-derived OC was preserved preferentially the most in the MAOM. Straw incorporation increased the soil nutrient content and stimulated the microbial activity, resulting in greater increases in microbial necromass C accumulation in POM and MAOM (by 117% and 43%, respectively) compared to biochar (by 72% and 18%). Moreover, straw incorporation promoted poorly crystalline (Feo) and organically complexed (Fep) Fe oxides accumulation, and both were significantly and positively correlated with MAOM and SOC. The results address the decadal-scale effects of biochar and straw application on the formation of the stable organic C pool in soil, and understanding the causal mechanisms can allow field practices to maximize SOC content. These results are of great implications for better predicting and accurately controlling the response of SOC pools in agroecosystems to future changes and disturbances and for maintaining regional C balance.

Valence fixable ferrozine gel rod combined with smartphone for facile determination of redox-active Fe2+ in environmental water

Ferrous ion (Fe2+) can indicate the redox situation of water and also plays an important role in maintaining the ecological balance of water bodies. However, due to the redox-active property of Fe2+, it is still a huge challenge to sensitively and accurately determine Fe2+ especially in interstitial water. Herein, we prepared a ferrozine gel rod for valence fixation during sampling and subsequent smartphone-based detection of Fe2+. The electrode potential of the redox pair can be varied through the formation of Fe2+-ligand complexes, and when Ecomplex was higher than EO2/OH−, the oxidation of Fe2+ by O2 was hindered, thus achieving the valence fixation of Fe2+. Six ligands were screened, and it was found that ferrozine could effectively increase the redox potential after complexing with Fe2+, and also exhibits an obvious color change while fixing the valence of Fe2+. To facilitate Fe2+ detection, a cross-linked porous polymer gel rod prepared by acrylamide and sodium alginate was used to encapsulate the ferrozine molecules. The ferrozine gel rod enabled fixation the valence of Fe2+ longer than 30 days, and the resulted purple-red color was pictured and analyzed by a smartphone. Ultimately, the developed ferrozine gel rod sensing system was able to achieve sensitive and linear detection of Fe2+ in the range of 1–200 μM with the limit of detection as low as 0.33 μM, and it also exhibited excellent selectivity and anti-interference ability. The accuracy and reliability of the method was verified by the determination of Fe2+ in spiked water samples and certified standard reference water samples. Finally, the ferrozine gel rod sensing system was successfully applied to in-situ detection of Fe2+ in interstitial water, overlying water and upper water of lake and river. This facile system that enabled valence fixation and fast detection is promising for detection of Fe2+ in environmental waters.

Microbial magnetite oxidation via MtoAB porin-multiheme cytochrome complex in Sideroxydans lithotrophicus ES-1.

Mineral-bound iron could be a vast source of energy to iron-oxidizing bacteria, but there is limited evidence of this metabolism, and it has been unknown whether the mechanisms of solid and dissolved Fe(II) oxidation are distinct. In iron-reducing bacteria, multiheme cytochromes can facilitate iron mineral reduction, and here, we link a multiheme cytochrome-based pathway to mineral oxidation, broadening the known functionality of multiheme cytochromes. Given the growing recognition of microbial oxidation of minerals and cathodes, increasing our understanding of these mechanisms will allow us to recognize and trace the activities of mineral-oxidizing microbes. This work shows how solid iron minerals can promote microbial growth, which if widespread, could be a major agent of geologic weathering and mineral-fueled nutrient cycling in sediments, aquifers, and rock-hosted environments.

Paleo-redox conditions during the demise of a carbonate platform in the Tethyan ocean: Evidence from phosphatized and metals (Mn and Fe) rich hardgrounds

Phosphatized Mn and Fe rich hardgrounds and condensed pelagic deposits in carbonate platform successions are precious archives of abrupt climate and environmental changes (redox conditions and phosphorous availability) in the past shallow-water marine environment. While numerous examples have been documented in the Cretaceous successions of the Northern Tethys, the scarcity of similar descriptions from the southern margins suggests differences in sedimentary processes or preservation conditions.In this work we study three phosphatized Mn and Fe rich hardgrounds and pelagic condensed deposits that mark the repetitive demise of the Panormide carbonate platform developed in the Southern Tethyan margin during the Cretaceous. The integration of SEM-EDS, PXRD, and Micro-Raman spectroscopy data shows that these hardgrounds consist of fine-grained Fe (goethite and hematite) and Mn (birnessite and/or vernadite) oxides dispersed in a calcite and apatite matrix. Micro-Raman spectroscopy shows the presence of oxidized Mn species: Mn3+ and Mn4+. The oxidation of Mn2+ → Mn3+/4+ and/or Fe2+ → Fe3+ occurred at the sediment-seawater interface under oxic conditions (where both Mn and Fe oxidize) or suboxic conditions (where only Fe oxidizes). The paleoenvironmental perturbations that triggered the formation of both hardgrounds and condensed pelagic deposits were likely related to pCO2 cycle, upwelling of P-Mn-Fe-rich water masses, eutrophication and phosphatization related to the Cretaceous climate oscillations during the main Oceanic Anoxic Events. These perturbations were likely enhanced by tectonic activity. Moreover, we show that the formation of the phosphatized metals-rich hardgrounds and the recovery of shallow-water sedimentation occurred after long-term periods (6–12 Ma). Thus, the Panormide serves as a remarkable example of resilience amidst significant climatic changes.

Enhanced phosphorus removal from anoxic water using oxygen-carrying iron-rich biochar: Combined roles of adsorption and keystone taxa

Anthropogenic enrichment of phosphorus (P) in water environment can cause eutrophication, harmful algal blooms, and water quality deterioration. Adsorbents are often used for the removal and recovery of P from water, however, P is highly susceptible to re-release in anoxic benthic environments. As a response, this study prepared oxygen-carrying iron-rich biochar (O-Fe-BC) as an effective oxygen micro-nanobubble carrier (Q = 8.7024 cm³/g STP at 1.5 MPa) and P adsorbent (qm = 16.7097 mg P/g, q0.1 = 3.1974 mg P/g). Over the 90-day experimental period with O-Fe-BC, dissolved oxygen (DO) levels in the overlying water could maintain at ∼4 mg/L (peaking at ∼9.5 mg/L), and total phosphorus (TP) and soluble reactive phosphorus (SRP) levels decreased by over 96 %. The higher inorganic phosphorus content in the surface sediment-biochar mixture, along with the lower labile P and Fe concentration in the sediment pore water in the O-Fe-BC group compared to other groups, suggested the enhanced P immobilization. Further mechanism exploration revealed the combined roles of adsorption and microbial response, in which O-Fe-BC achieved efficient phosphate adsorption primarily through inner-sphere complexation via ligand exchange and keystone taxa (particularly Candidatus Electronema) played a crucial role in driving water chemistry divergence. Specially, these cable bacteria could provide large pools of Fe oxides in the surface sediment, binding with P to prevent its release, as supported by significant correlations between Ca. Electronema abundance and oxidation–reduction potential (ORP), TP, SRP, and sediment Fe-P variations. Additionally, a pot experiment with mung bean seedlings showed that the recovered O-Fe-BC significantly promoted the seed germination and growth, indicating its potential as a novel material for removing and recovering P from eutrophic waters. Taken together, our work provided a promising strategy for sustainable anoxia and P pollution mitigation, and also highlighted the indispensable roles of inner-sphere adsorption in P recovery and microbial keystone taxa in P cycling regulation.

Microbial cycling contributes to the release of dissolved inorganic phosphate into the groundwater of floodplain aquifers

Little is known about biological processes controlling inorganic phosphate (PO4) in groundwater ecosystems. Here we present analyses of groundwater samples from the Hetao Basin, China that show an increasing contribution of microbial cycling to groundwater PO4 from oxic to anoxic conditions along a flow path with phosphate-bound oxygen isotopes (δ18OPO4). Under oxic conditions, although 25–47% of the dissolved PO4 inherited the initial source signal of igneous apatite, groundwater δ18OPO4 reflected a pronounced impact of intracellular enzymatic cycling. Under anoxic conditions, dissolved PO4 carried a nearly exclusive equilibrium isotope signal, which was probably due to (i) release of PO4 with an equilibrium δ18OPO4 from Fe(III) oxides, as a result of Fe(III) reduction in the presence of Fe(III)- and sulfate-reducing bacteria; and/or (ii) cumulative microbial cycling of dissolved PO4 with increasing groundwater residence time. Our study highlights that PO4 in groundwater is tightly microbially cycled under a wide range of redox conditions and microbial cycling contributes to the release of PO4 in groundwater.

Simultaneously reducing methane emissions and arsenic mobility by birnessite in flooded paddy soil: Overlooked key role of organic polymerisation

Flooding of paddy fields enhances methane (CH4) emissions and arsenic (As) mobilisation, which are crucial issues for agricultural greenhouse gas emissions and food safety. Birnessite (δ-MnO2) is a common natural oxidant and scavenger for heavy metals. In this study, birnessite was applied to As-contaminated paddy soil. The capacity for simultaneously alleviating CH4 emissions and As mobility was explored. Soil microcosm incubation results indicated that birnessite addition simultaneously reduced CH4 emissions by 47 %–54 % and As release by 38 %–85 %. The addition of birnessite decreased the dissolved organic carbon (DOC) contents and altered its chemical properties. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) results showed that birnessite reduced the labile fractions of proteins, carbohydrates, lignins, tannins, and unsaturated hydrocarbons, however, increased the abundance of condensed aromatic structures, suggesting the polymerisation of dissolved organic matter (DOM) by birnessite. The degradation of labile fractions and the polymerisation of DOM resulted in an inventory of recalcitrant DOM, which is difficult for microbes to metabolise, thus inhibiting methanogenesis. In contrast, birnessite addition increased CH4 oxidation, as the particulate methane monooxygenase (pmoA) gene abundance increased by 30 %. The enhanced polymerisation of DOM by birnessite also increased As complexation with organics, leading to the transfer of As to the organic bound phase. In addition, the decrease in ferrous ion [Fe(II)] concentrations with birnessite indicated that the reductive dissolution of Fe oxides was suppressed, which limited the release of arsenite [As(III)] under reducing conditions. Furthermore, birnessite decreased As methylation and shaped the soil microbial community structure by enriching the metal-reducing bacterium Bacillus. Overall, our results provide a promising method to suppress greenhouse gas emissions and the risk of As contamination in paddy soils, although further studies are needed to verify its efficacy and effectiveness under field conditions.

Energy Evaluation and Mathematical Modeling of Pellet Production from Metal-Bearing Waste with a Focus on Alternative Applications of Reducing Agents

The authors of this study focused on the energy and material assessment of processes for processing pellets from metal-bearing waste, specifically Fe concentrate. A mathematical model was created for process evaluation, with which thermotechnical calculations of parameters in the processing of metallized pellets were carried out. Thermodynamic calculations were performed to determine the enthalpy of the charge in individual devices (drying chamber, rotary kiln, cooler). For the reduction of Fe oxides, carbon from coke (with Fe oxide reductions of 50%, 61%, and 92%) and lignite (with Fe oxide reductions of 69% and 92%) were considered as part of the pellets. The degree of reduction of iron oxides was a determining parameter, and the consumption of the reducing agent corresponded to the direct reduction of Fe oxides by carbon with a coefficient of 1.5. Another determining parameter was the input and output temperature in individual devices. For a more precise description of the processes in individual devices, calculations were carried out zonally. The results of the calculations are analyses and recommendations for feasible alternatives for the reducing agent and associated processes.

Iron‑carbon complex types and bonding forms jointly control organic carbon mineralization in paddy soils

The crucial role of iron (Fe) oxides in stabilizing soil organic carbon (SOC) is well recognized, but their effects on SOC mineralization remain poorly understood. To address this knowledge gap, we evaluated the effects of four typical Fe-bound OC (Fe-OC) complexes including adsorbed ferrihydrite (Fh)- and goethite (Goe)- 13C, coprecipitated Fh/Goe-13C and 13C-glucose as the control, on OC mineralization during an 80-day anaerobic incubation in a paddy soil. 13C-tracing indicated that Fe-13C complexes significantly stimulated CO2 emissions from both the input 13C and SOC compared with glucose alone. In contrast, the addition of Fh- and Goe-C complexes consistently inhibited CH4 emissions by 72–91 % and 21–61 % compared with glucose addition, respectively. Fe-OC complexes reduced the CO2 equivalent by 62–71 % and 17–41 % in soils with Fh-C and Goe-C complexes, respectively. We concluded that Fe crystallinity and its bonding forms with organic carbon jointly control SOC mineralization. The coprecipitated Goe-C complexes had the lowest OC mineralization rate and highest OC residence time among four Fe-OC complexes. These findings highlighted that promoting the formation of coprecipitated well-ordered minerals would increase SOC sequestration by reducing OC mineralization and mitigating the global warming effect in paddy management.

Phosphate ligand-mediated production of reactive oxygen species during oxygenation of Fe(II)-phosphate complexes

Reactive oxygen species (ROS) production upon the oxygenation of reduced iron minerals is of critical importance to redox cycles of Fe and the fate of refractory organic contaminants. The environmental impact factors during this process, however, have been underappreciated. In this study, prominently enhanced production of hydroxyl radicals (•OH) was observed by oxygenation of Fe(II) with 5–50 mM phosphate. The results of spin trap electron spin resonance (ESR) experiment showed that Fe(II)-phosphate complexes facilitated the generation of •OH. The degradation experiment of p-nitrophenol (PNP) confirmed that •OH formation was dominated by a consecutive one-electron O2 reduction (90.2–96.9 %), and the quantification of PNP degradation products revealed that Fe(II)/phosphate molar ratios regulated the O2 activation pathways for O2•− or •OH production. The further experimental and theoretical investigation demonstrated that the coordination of phosphate with Fe(II) plays a dual role in ROS generation that facilitated O2•− formation by lowering the energy barrier for Fe(II) oxidation and altered the reaction pathway of •OH formation due to its occupation of sites for electron transfer. The present work highlights an important role of natural oxyanions in O2 activation by Fe(II) and raises the possibility of in situ degradation of contaminants in subsurface environment.

Characterization of regolith-hosted rare earth element deposits using reflectance spectroscopy: Framework towards an efficient and reliable field exploration tool

With a growing demand for the rare earth elements (REE), exploration of regolith-hosted REE resources worldwide has been thriving in recent years and development of a rapid and reliable field-based tool will greatly facilitate the survey and exploration. In this study, we use visible and short-wave infrared (VNIR-SWIR) reflectance spectroscopy to comprehensively evaluate the applicability of the technique to explore regolith-hosted REE resources, exemplified by three representative regolith-hosted REE deposits in China. Neodymium among the REE shows reliably detectable spectral features in the VNIR-SWIR spectroscopy down to concentrations of 10–50 ppm in field samples with heterogeneous mineral grain sizes. The Nd spectral intensity of electronic transition at the band of ∼800 nm is correlated with bulk Nd concentrations and can be used as semi-quantitative indicators for the Nd concentrations, thereby the total REE in regolith. Moreover, VNIR-SWIR spectroscopy is demonstrated to be capable of delineating favorable ore-bearing mineralogy by characterizing the abundance and type of clay minerals and Fe (oxyhydr)oxides, and the crystallinity of kaolinite-group minerals. However, the Nd spectral features of samples with high bulk Fe2O3 contents (>3 wt%) are significantly masked due to overlapping by the strong absorption features of ferric (oxyhydr)oxides. VNIR-SWIR spectroscopy is deemed to be applicable to the exploration of regolith-hosted REE resources developed from Fe-poor felsic rocks.

Antisolvent crystallization of rare earth sulfate hydrates: Thermodynamics, kinetics and impact of iron

The thermodynamics and kinetics of ethanol antisolvent crystallization of rare earths from sulfate solutions has been explored, with a view towards separating the rare earths as part of a NdFeB magnet recycling process. The solubility of single and binary metal (Nd, Pr, Fe) phases in aqueous ethanol solutions has been determined. The impact of Fe and Pr on the crystallization of Nd is evaluated, the oxidation kinetics of Fe(II) to Fe(III) quantified, and the influence of Fe oxidation state on the thermodynamics and kinetics of crystallization investigated. Oxidation to Fe(III) is slow, with a half life of approx. 600 h. For pure Nd, the solubility of the obtained, stable sulphate octahydrate decreases exponentially with increased molar organic:aqueous (O/A) ratio, and is well described by the OLI model until O/A=0.2. Pr crystallizes as an isostructural octahydrate with similar solubility. Fe(II) precipitates as a mixed solid phase, with a solubility approximately 40 times higher than the rare earths at O/A=0.2. Fe(III) solutions exhibit liquid–liquid phase separation without precipitation at all evaluated concentrations. Nd and Pr coprecipitate together in proportion to their relative concentrations, with Pr precipitating at concentrations well below its pure component solubility. Fe(II) does not precipitate with Nd at O/A≤0.2 even at high concentration, with significant precipitation as separate particles at higher O/A for all concentrations. The crystallization kinetics and the morphology of the Nd phase is affected by the Fe oxidation state. The work highlights the potential of antisolvent crystallization for selective and efficient separation of REE from Fe.

Effect of Vegetation Restoration on Soil Iron‐Associated Carbon Dynamics: Insights From Different Soil Textures

AbstractSoil iron (Fe)‐associated carbon (C) (Fe‐OC) plays a vital role in the soil C cycle due to its high stability, but vegetation restoration might alter the composition and quantity of Fe‐OC by introducing a large amount of plant‐derived C and affecting soil properties. However, how vegetation restoration affects soil Fe‐OC remains unclear. Herein, plant and topsoil samples from grasslands, shrublands, and forestlands across three soil types (loam, loess, and sandy soil) since cropland conversions were collected to address this issue. The results showed soil Fe‐OC content decreased in loam soil but increased in loess and sandy soil following vegetation restoration. Additionally, the Fe‐OC accumulation efficiency induced by vegetation restoration increased with the coarser soil texture. Vegetation restoration promoted the accumulation of Fe‐OC by increasing soil microbial biomass C, dissolved organic C, aromatic‐C, and citric acid, but also disrupted the combination of Fe oxides and C by introducing oxalic acid, reducing Fe oxide content and iron trivalent (Fe(III)). There were two‐sided effects of vegetation restoration on Fe‐OC, but the overall effect depends on the soil types. Moreover, isotopic evidence indicated that microbial source C is the main source of Fe‐OC, but Fe oxides preferentially adsorbed dissolved organic matter (DOM) and root deposits from plants rather than microbial residues and metabolites following vegetation restoration. In addition, Fe oxides preferentially adsorbed aromatic‐C compared to other functional group components. These findings indicated that vegetation restoration in coarser‐texture soils, coupled with selecting species that increase soil microbial biomass, produce more root deposits, and enhance DOM, contribute to the accumulation of soil Fe‐OC.

Migration and controlling factors of rare earth elements in geothermal systems on the southern Tibetan Plateau

Rare earth elements (REE) serve as effective tracers of water-rock interactions, a crucial process in the evolution of geothermal systems. However, the geochemical behavior of REE during their migration within geothermal systems, particularly the fractionation mechanism, remains poorly understood. In this study, we focus on the geochemical characteristics of REE in hot springs, host rocks, and sinters from various hot spring systems in the Yadong-Gulu rift (YGR), the largest extensional rift in the southern Tibetan Plateau. The objective is to explore the factors that control REE concentrations in hot springs and elucidate the fractionation of REE during their migration. The concentrations of REE are significantly influenced by pH, Fe oxides (oxyhydroxides), and HCO3− concentrations in central and southern hot springs, whereas high reservoir temperatures contribute to higher ΣREE concentrations in northern hyperthermal springs. REE speciation calculations show that LnO2− and LnO2H are dominant complexes in northern alkaline hot springs, while carbonate complexes (LnCO3+ and Ln(CO3)2−) prevail in central and southern spring samples. Additionally, weakly acidic hot springs exhibit a prevalence of Ln3+, LnF2+, and LnSO4+ species. The chondrite-normalized REE patterns of all hot spring samples display enrichment in MREE, which is significantly distinct from the patterns observed in host rocks and sinters enriched in LREE. The fractionation of REE in the YGR hot spring systems is primarily controlled by the following processes: (1) Temperature, pH, and relative abundance of complexing agents influence the complexation of REE and further regulate their fractionation in hot springs; (2) During water-rock interaction, preferential leaching of HREE and MREE from host rocks can lead to their enrichment in alkaline hot springs. The dissolution of iron-rich sediments plays a significant role in generating the distinctive MREE bulge pattern in acid-neutral hot springs compared to host rocks; (3) The higher stability of MREE and HREE complexes in water, as well as the preferential coprecipitation of unstable LnCO3+ complexes formed by LREE with carbonates, are key factors responsible for LREE enrichment in sinters.

Tree species identity affects soil P bioavailability by altering labile organic P after tree mixing in subtropical China

AbstractConverting monocultures to mixed plantations has been emphasized to improve ecosystem productivity and services. However, the impact of tree species identity on phosphorus (P) bioavailability in acidic soils in subtropical China, where P is relatively scarce, is not fully understood. This study explored the changes in soil biologically‐based P fractions and the effect of mineral and microbial properties on P transformation after mixing five broadleaved trees (Bretschneidera sinensis, Manglietia conifera, Cercidiphyllum japonicum, Michelia maudiae and Camellia oleifera) individually with coniferous trees (Pinus massoniana). The results showed that most mixed plantations significantly increased pH and citric acid and decreased exchangeable Fe3+ and Al3+ and the activation of Fe and Al oxides compared with monospecific plantations, which significantly reduced P precipitation and adsorption. Mixed planting significantly increased phosphatase activity and altered the community composition of P‐mobilizing bacteria carrying phoD and pqqC genes, which contributed to organic P mineralization and inorganic P (Pi) desorption. Mixed planting increased microbial biomass and the relative rate of microbial biomass P turnover. Labile organic P (Enzyme‐P) was a potentially significant source of soluble Pi (CaCl2‐P) among the biologically‐based P fractions, plus microbial biomass P. Overall, introducing broadleaved species, especially in species (e.g. Cercidiphyllum japonicum, Michelia maudiae and Camellia oleifera) with relatively high litter quality and belowground secretions (e.g. citric acid, phosphatase), significantly increased the solubilization of recalcitrant Pi (HCl‐P), desorption of chemisorbed Pi (Citrate‐P) and accumulation and mineralization of Enzyme‐P, thereby increasing the available P pools. Redundancy analysis demonstrated that P fractions were mainly driven by phosphatases, exchangeable cations, floor fresh litter lignin/N and citric acid. Altogether, we highlight the importance of choosing tree species mixtures that have synergistic or complementary effects when constructing mixed plantations in order to alleviate soil P limitations.

Metagenomic analysis reveals enhanced sludge dewaterability through acidified sludge inoculation: Regulation of Fe (II) oxidation electron transport pathway

The bioleaching utilizing indigenous microbial inoculation can continuously improve the dewaterability of sludge. In this study, metagenomic analysis was innovative employed to identify the key microorganisms and functional genes that affect the dewatering performance of sludge in the bioleaching conditioning process. The results demonstrated that long-term repeated inoculation of acidified sludge resulted in increased abundance of many functional genes associated with the transport of carbohydrate and amino acid. Additionally, genes encoding key iron transport proteins (such as afuA, fhuC, and fhuD) and genes related to electron transfer carriers in ferrous iron oxidation process (such as rus and cyc2) were significantly enriched, thereby promoting the improvement of sludge dewatering performance through enhanced iron oxidation. Notably, Acidithiobacillus, Betaproteobacteria, and Hyphomicrobium were the major sources of functional genes. This study reveals the microscopic mechanisms underlying the improvement of sludge dewaterability through bioleaching based on mixed culture from a novel perspective of gene metabolism.

Mechanistic analysis of hydrogen-rich Co-gasification of pine wood and polypropylene-based waste masks using Fe/Dol catalyst

Disposable masks, predominantly made of polypropylene melt-blown fabric, present a significant environmental challenge due to their large volume and resistance to natural degradation. This study explores the co-gasification of forestry waste, specifically pine wood, and waste masks to enhance biomass gasification efficiency while enabling the high-value utilization of waste materials. The Fe/Dol catalyst, prepared by loading transition metal Fe onto calcined dolomite using the impregnation method, was tested in a two-stage fixed-bed gasification system. Steam was employed as the gasifying agent. The study systematically examines the effects of steam flow rate, gasification reforming temperature, the mixing ratio of pine wood to masks, and Fe loading on the catalyst's performance in gas-phase and liquid-phase product formation.Characterization analyses revealed that Fe oxides facilitate the cleavage of aromatic rings in aromatic compounds, leading to the formation of two-carbon chain segments and promoting the production of ethylene and propylene from aliphatic hydrocarbons. Additionally, the catalyst enhanced tar cracking, generating free radicals and ring bonds. Experimental results indicate that at a steam flow rate of 3 mg/min, a gasification temperature of 850 °C, a pine wood to mask mixing ratio of 1:2, and an Fe loading of 8 %, the hydrogen (H2) volume fraction reached 52.48 %, with a gas yield of 1.67 m³/kg and a hydrogen production rate of 78.25 g/kg.

Intense intrusion of low-oxygen waters into mid-Cambrian surface ocean carbonate factories

The Phanerozoic surface ocean is characterized by its high dissolved oxygen content owing to mixing with the atmosphere. However, atmospheric oxygen levels varied in the early Paleozoic and it remains unclear whether the surface ocean was susceptible to significant redox fluctuations in response to extreme environmental events. In this study, we probed the redox structures of shallow middle Cambrian marine depositional environments across the North China Platform, ranging from open tidal flats to relatively deep subtidal environments. We utilized a combination of least diagenetically altered carbonate materials (such as ooid cortices, calcimicrobes, and their fringing cements), as well as in situ element measurement and imaging techniques. By analyzing a set of redox-related elements (e.g., Ce anomaly, Zn/Fe molar ratio, Mn and Cr) and mineralogical proxies (hydrogenetic Fe oxides), we revealed a stratified redox structure in the Drumian surface oceans. Compared to earlier Drumian conditions, late Drumian surface oceans experienced significant intrusions of ferruginous waters, probably reaching into shallow subtidal environments with water depths less than 10 m. Furthermore, we identified shallow subtidal microbial O2-producing factories, characterized by dendritic Epiphyton thalli. These calcimicrobes exhibited more oxygenated signatures (negative Ce anomalies and enrichment of hydrogenetic Fe oxides) relative to contemporaneous less oxic shallower and deeper environments. This finding indicates that they produced oxygen oases or refuges during periods of both normal and poor dissolved O2 conditions. This study has the potential to broaden our understanding of redox conditions and microbial oxygen-producing mechanisms in the surface ocean, particularly during intervals characterized by low atmospheric oxygen levels or episodic anoxic events.

Highly efficient removal of aqueous phosphate via iron-manganese fabricated biochar: Performance and mechanism

Biochar (BC) has emerged as a potential solution to phosphate removal from wastewater primarily resulting from global overuse of fertilizers. Further modification by embedment of iron (Fe)-manganese (Mn) oxides on BC can enhance phosphate removal; however, the modification method serves as a vital factor underlying distinctive removal performances and mechanisms, which have yet been systematically examined. Herein, two Fe–Mn modified BC, Fe/MnBC (comprised of Fe3O4 and MnO2) and Fe–MnBC (comprised of MnFe2O4), were comprehensively investigated for gaining insights into the unsolved perspectives. The results indicated that Fe–MnBC exhibited a markedly greater maximum phosphate adsorption capacity of 135.88 mg g−1 than that of Fe/MnBC with 17.93 mg g−1. The comparative results based on microstructure and spectroscopic analyses suggested that different Fe and Mn oxides were successfully loaded, which played a distinctive role in phosphate removal. Further characterizations unveiled that the key mechanisms for phosphate removal by Fe/MnBC are inner-sphere complexation and precipitation, while electrostatic interaction and outer-sphere complexation are the dominant mechanisms underlying the notable performance of Fe–MnBC. The delicately designed Fe–MnBC with special structure and property also enabled a superior regeneration capacity, which presented a promisingly high phosphate removal efficacy of over 81.34% after five cycles. These results enhance comprehension regarding the impact of biochar modification techniques on phosphate removal, offering positive indications for the remediation of excessive phosphate and other pollutant-containing water through feasible design and green chemicals.