Transformation Of Iron Oxides Research Articles

Effects of low-molecular-weight organic acids on the transformation and phosphate retention of iron (hydr)oxides

The retention and mobilization of phosphate in soils are closely associated with the adsorption of iron (hydr)oxides and root exudation of low-molecular-weight organic acids (LMWOAs). This study investigated the role of LMWOAs in phosphate mobilization under incubation and field conditions. LMWOAs-mediated iron (hydr)oxide transformation and phosphate adsorption experiments revealed that the presence of LMWOAs decreased the phosphate adsorption capacity of iron (hydr)oxides by up to ~74 % due to the competition effect, while LMWOAs-induced iron mineral transformation resulted in an approximately six-fold increase in phosphate retention by decreasing the crystallinity and increasing the surface reactivity. Root simulation in rhizobox experiments demonstrated that LMWOAs can alter the contents of different extractable phosphate species and iron components, leading to 10 % ~ 30 % decreases in available phosphate in the near root region of two tested soils. Field experiments showed that crop covering between mango tree rows promoted the exudation of LMWOAs from mango roots. In addition, crop covering increased the contents of total phosphate and available phosphate by 9.08 % ~ 61.20 % and 34.33 % ~ 147.33 % in the rhizosphere soils of mango trees, respectively. These findings bridge the microscale and field scale to understand the delicate LMWOAs-mediated balance between the retention and mobilization of phosphate on iron (hydr)oxide surface, thereby providing important implications for mitigating the low utilization efficiency of phosphate in iron-rich soils.

Effects of flooding and warming on soil nitrogen fraction transformation under low‐molecular‐weight organic acid inputs

AbstractFlooding and climate warming lead to the increase of low‐molecular‐weight organic acid (LMWOA) inputs to soil. However, it is unclear what the effects of flooding and climate warming on soil nitrogen fraction transformation under LMWOA input are. Fluvisol was collected in the riparian zone of the Three Gorges Reservoir to conduct an incubation experiment with the treatments of three LMWOAs at five contents, two hydrological environments and two temperatures. Compared with LMWOA input of 0 mg kg−1, the soil nitrogen in ion exchangeable fraction (IEF‐N), strong oxidant extractable fraction (SOEF‐N) and non‐transformable nitrogen (NTF‐N) were increased by 35.77, 54.71 and 25.49 mg kg−1, respectively, under LMWOA input of 40 mmol kg−1. Soil nitrogen in the weak acid extractable fraction (WAEF‐N) was decreased by 117.41 mg kg−1. Microbial biomass nitrogen (MBN) was increased by 25.29 mg kg−1, and calcium carbonate (CaCO3) was decreased by 8.03 g kg−1. The contents of IEF‐N, NTF‐N and amorphous iron oxides were higher under the flooding environment than under the drying environment. In contrast, opposite results were observed for soil nitrogen in the strong alkali extractable fraction (SAEF‐N), SOEF‐N and MBN. IEF‐N and NTF‐N contents were higher at 20°C than at 30°C, and the contents of SOEF‐N and MBN were higher at 30°C than at 20°C. WAEF‐N was dissolved by LMWOA through CaCO3 dissolution. The dissolved WAEF‐N was partly transformed into SOEF‐N and NTF‐N by microbial assimilation and humification. Flooding desorbed SAEF‐N through the crystalline transformation of iron oxides. Flooding inhibited the transformation of IEF‐N to SOEF‐N and promoted the formation of NTF‐N, while warming did the opposite. The results provide a perspective of the bound state between soil and nitrogen for understanding the soil nitrogen cycling and help to assess the impacts of climate warming and flooding on soil nitrogen loss from soil to the surrounding water.

The fate of Arsenic associated with the transformation of iron oxides in soils: The mineralogical evidence

The influence of iron (oxyhydr)oxides on the transformation and migration of arsenic(As) has garnered significant attention. Previous work has largely focused on the transformation of iron oxides related to As fate at molecular and mechanistic levels. However, studies examining the interplay between As concentration and iron oxides transformation within complex soil system are sparse. This study investigates the transformation of iron oxides in soils with varying As concentration during microbial dissimilatory iron reduction (DIR), employing humic acid (HA) as electron shuttle and assesses the impact on As speciation transformation. Comparative analyses indicate that in soils with high As concentration (>1000 mg/kg), the secondary transformation of iron (oxyhydr)oxides to other forms, such as the conversion of ferrihydrite to goethite and lepidocrocite, or schwertmannite to goethite, is impeded. Consequently, the formation of goethite and lepidocrocite, which would typically re-stabilize As, is inhibited, leading to elevated release of As(III). On the other hand, an increase in magnetite formation in soils with low As concentration (<100 mg/kg) appears to re-stabilize As effectively. Furthermore, the formation of new secondary iron (oxyhydr)oxides in soils with As concentration <200 mg/kg enhances fraction F5, which subsequently contributes to the re-immobilization of As, sequestering it within the soil matrix. This process results in a lower release of As(III) from soils with As concentration below 200 mg/kg. These findings enhance the understanding of the interdependent relationship between the transformation of iron oxides and the fate of As in complex soil systems.

Effects of carbonate on ferrihydrite transformation in alkaline media.

Alkaline media widely exist in natural and engineered systems such as semiarid/arid areas, radioactive waste sites, and mine tailings. In these settings, the commonly occurring iron (oxyhydr)oxides differed in their ability to influence the fate of nutrients and contaminants. Due to the substantially increased atmospheric carbon dioxide (CO2) concentration, carbonate stands to increase in these media. However, how increasing carbonate affects the transformation of poorly crystalline iron (oxyhydr)oxides (e.g., two-line ferrihydrite) under alkaline conditions still remains unclear. Here, kinetics of ferrihydrite transformation were evaluated at pH ∼10 as a function of [carbonate] = 0-286 mM using synchrotron-based X-ray and vibrational spectroscopic techniques. The results showed that carbonate slowed down ferrihydrite transformation slightly and suppressed goethite formation, but promoted hematite formation regardless of its concentration. At low carbonate concentration (11.42 mM), the effect of carbonate on product formation was obvious due to the weak inner-sphere complex; however, at high carbonate concentration (80-286 mM), the effect was retarded because of the adsorption equilibrium of carbonate as well as the initial carbonate adsorption followed by desorption. Moreover, carbonate modified the morphology of hematite from rhombic to ellipsoidal to honeycomb and goethite from rod-like to needle-like to spindle-like due to the inner-sphere adsorption-desorption of carbonate and adsorption of hydroxyl ions on reactive sites of iron (oxyhydr)oxides in alkaline media. The results suggest that the concurrently increasing carbonate with enhanced atmospheric CO2 could control the transformation and occurrence of iron (oxyhydr)oxides in natural and engineered environments and have important implications for the biogeochemical cycles of iron and carbon.

Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption

Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption

Iron (hydr)oxide dynamic transformation-induced perfluorooctanoic acid transport and attenuation effect: Impacts of initial goethite and associated minerals content and groundwater type

Perfluorooctanoic acid (PFOA) has been widely utilized, leading to serious contamination. Iron (hydr)oxide transformation was varied in media. Whereas, dynamic transformation effect was extensively unclear. Here, iron (hydr)oxide dynamic transformation-induced PFOA transport and attenuation was investigated by emphasizing initial goethite (α-FeOOH) and associated minerals content and groundwater type based on the multi-process attenuation model. Results revealed that groundwater type did not affect the PFOA attenuation pathway. However, it controlled the iron (hydr)oxide dynamic transformation differences. PFOA transport behavior (retardation factor R from 2.61 to 1.91) was significantly affected by iron (hydr)oxide dynamic transformation. Iron (hydr)oxide transformation induced the greatest PFOA transport risk (R = 1.91, attenuation rate λ = 0.0001 min−1) in SO42− environment, where complex α-FeOOH, Fe3O4, and β-Fe2O3·H2O transformed to simplex β-FeOOH, leading to instantaneous (Kd) and kinetic (α) two-site sorption fraction change. Furthermore, the associated mineral Fe3O4 of goethite was crucial in PFOA attenuation (λ from 0.0001 to 0.0002 min−1). Fe3O4 released Fe2+ and the oxidation of Fe2+ to Fe3+ provided electrons, facilitating the formation of F–(CF2)7–COO· radicals, which played a key role in the following cycle attenuation process. This study provides a theoretical basis for understanding the interaction mechanism of PFOA and iron (hydr)oxide dynamic transformation under groundwater differences.

Unraveling the roles of microporous and micro-mesoporous structures of carbon supports on iron oxide properties and As (V) removal performance in contaminated water

This study investigates the impact of microporous (SP–C) and micro-mesoporous carbon (DP-C) supports on the dispersion and phase transformation of iron oxides and their arsenic (V) removal efficiency. The research demonstrates that carbon-supported iron oxide sorbents exhibit superior As(V) uptake capacity compared to unsupported Fe2O3, attributed to reduced iron oxide crystallite sizes and As(V) adsorption on carbon supports. Maximum As(V) uptake capacities of 23.8 mg/g and 18.9 mg/g were achieved for Fe/SP-C and Fe/DP-C at 30 wt% and 50 wt% iron loading, respectively. The study reveals a nonlinear relationship between As(V) sorption capacity and iron oxide crystallite size after excluding As(V) adsorption capacity on carbon supports, suggesting the iron oxide phase (Fe3O4) plays a role in determining adsorption capacity. Iron oxide-loaded DP-C sorbents exhibit faster adsorption rates at low As(V) concentrations (5 mg/L) than SP-C sorbents due to their bimodal pore structure. Adsorption behavior varies at higher As(V) concentrations (45 mg/L), with Fe/DP-C reaching maximum capacity more slowly due to limited available adsorptive sites. All adsorbents maintained near-complete As(V) removal efficiency over five cycles. The findings provide insights for designing more efficient adsorbents for As(V) removal from contaminated water sources.

Cooperative effect of slow-release ferrous and phosphate for simultaneous stabilization of As, Cd and Pb in soil

The different chemical behavior of anionic As and cationic Cd and Pb makes the simultaneous stabilization of soils contaminated with arsenic (As), cadmium (Cd), and lead (Pb) challenging. The use of soluble, insoluble phosphate materials and iron compounds cannot simultaneously stabilize As, Cd, and Pb in soil effectively due to the easy re-activation of heavy metals and poor migration. Herein, we propose a new strategy of “cooperatively stabilizing Cd, Pb, and As with slow-release ferrous and phosphate”. To very this theory, we developed ferrous and phosphate slow-release materials to simultaneously stabilize As, Cd, and Pb in soil. The stabilization efficiency of water-soluble As, Cd and Pb reached 99% within 7d, and the stabilization efficiencies of NaHCO3-extractable As, DTPA-extractable Cd and Pb reached 92.60%, 57.79% and 62.81%, respectively. The chemical speciation analysis revealed that soil As, Cd and Pb were transformed into more stable states with the reaction time. The proportion of residual fraction of As, Cd, and Pb increased from 58.01% to 93.82%, 25.69 to 47.86%, 5.58 to 48.54% after 56 d, respectively. Using ferrihydrite as a representative soil component, the beneficial interactions of phosphate and slow-release ferrous material in stabilizing Pb, Cd, and As were demonstrated. The slow-release ferrous and phosphate material reacted with As and Cd/Pb to form stable ferrous arsenic and Cd/Pb phosphate. Furthermore, the slow-release phosphate converted the adsorbed As into dissolved As, then the dissolved As reacted with released ferrous to form a more stable form. Concurrently, As, Cd and Pb were structurally incorporated into the crystalline iron oxides during the ferrous ions-catalyzed transformation of amorphous iron (hydrogen) oxides. The results demonstrates that the use of slow-release ferrous and phosphate materials can aid in the simultaneous stabilization of As, Cd, and Pb in soil.

Enhanced degradation of microplastics during sludge composting via microbially-driven Fenton reaction

It has been increasingly documented that the hydroxyl radical (•OH) can promote the transformation of organic contaminants such as microplastics (MPs) in various environments. However, few studies have sought to identify an ideal strategy for accelerating in situ MPs degradation through boosting the process of •OH production in practical applications. In this work, iron-mineral-supplemented thermophilic composting (imTC) is proposed and demonstrated for enhancing in situ degradation of sludge-based MPs through strengthening •OH generation. The results show that the reduction efficiency of sludge-based MPs abundance was about 35.93% in imTC after treatment for 36 days, which was 38.99% higher than that of ordinary thermophilic composting (oTC). Further investigation on polyethylene-microplastics (PE-MPs) suggested that higher abundance of •OH (the maximum value was 408.1 μmol·kg−1) could be detected on the MPs isolated from imTC through microbially-mediated redox transformation of iron oxides, as compared to oTC. Analyses of the physicochemical properties of the composted PE-MPs indicated that increased •OH generation could largely accelerate the oxidative degradation of MPs. This work, for the first time, proposes a feasible strategy to enhance the reduction efficiency of MPs abundance during composting through the regulation of •OH production.

Iron (oxyhydr)oxides are responsible for the stabilization of Cu and Zn in AMD after treatment with limestone.

The formation and transformation of secondary iron (oxyhydr)oxides and their role in the stabilization of copper (Cu) and zinc (Zn) in acid mine drainage (AMD) after limestone treatment are worth studying to better understand the impacts of limestone AMD treatment. In this study, the wastewater from a copper mine ditch was sampled. Two different doses of limestone (S: 5.33 g L-1 and SS: 8.00 g L-1) were applied to adjust the pH range of the sampled AMD. The concentrations of Fe, Cu and Zn in the supernatant and the levels of iron (oxyhydr)oxides and heavy metals in AMD sediments were dynamically monitored for 300 days to analyze the transformation of the secondary iron mineral phase and the role iron (oxyhydr)oxides play in the removal and stabilization of Cu and Zn. The results showed that the pH rose rapidly to 6.82, decreased to 5.82 on the 150th day, and finally decreased to approximately 4.63 by the 300th day, when the dosage of limestone (S) was 5.33 g L-1. Goethite was the main form of iron oxides in the sediments. As the incubation time increased, so did the content of crystalline Fe (oxyhydr)oxides. In addition, the Cu and Zn content in the fraction of crystalline Fe (oxyhydr)oxides increased as the corresponding iron (oxyhydr)oxide increased. When the high dosage of limestone (8.00 g L-1 or SS) was applied, the pH remained at approximately at 7.46 during the whole period and goethite and lepidocrocite were present in the sediment. Amorphous/ poorly crystalline Fe-oxyhydroxide was the main product after SS limestone dosage, indicating that the risk of Cu and Zn reactivation in the sediment was higher with a higher limestone treatment dosage.

Green rust sulfate transformation under the impact of Cr(VI) and oxalic acid: Mechanism and environmental significance

Green rust (GR), as one of mixed-valent iron [Fe(II)-Fe(III)] minerals, has received a significant attention in recent years because it is an intrinsic and essential part of biogeochemical cycling of heavy metals and DOM. The transformation of GR is a key factor in altering the environmental behavior of heavy metals, and therefore, prediction of such transformation is critical for managing environmental quality. DOM and heavy metals are recognized to have a significant impact on iron oxide transformation. However, detailed information on these phenomena and mechanisms are still limited. In this study, Cr(VI) and oxalic acid (OA) widely distributed in the natural environment were selected representatives of heavy metals and DOM. The mechanism of their influence on GR transformation and their environmental significance were clarified. GR transformed to feroxyhyte under the impact of Cr(VI) and OA, and feroxyhyte did not transform to more crystalline iron oxides after 7 days. However, OA enhanced Fe dissolution and Cr(VI) reduction while weakening the immobilization of Cr on GR. SEM results demonstrated that OA addition resulted in the collapse of the feroxyhyte structure. SEM-EDS data indicated that Cr and OA were adsorbed on GR, suggesting that this can be an essential pathway for C and Cr sequestration during GR transformation. This study reveals Cr(VI) not only favors the formation of feroxyhyte, but also stabilizes the mineral to prevent transformation and meanwhile indicates the mechanisms of organic matter interactions with iron oxide and the environmental behavior of C and Cr during the iron oxide transformation processes.

Oxidative modification of industrial basic oxygen furnace slag for recover iron-containing phase: Study on phase transformation and mineral structure evolution

Basic oxygen furnace (BOF) slag is the main co-product in the steelmaking process, its recycling within the iron and steel enterprises is crucial for the industry to ensure greater sustainability. According to the composition characteristics of BOF slag, a method of separating and recovering iron resources by regulating the composition of BOF slag with silica as an additive at high temperature was proposed. In this study, the growth of iron-containing phase during oxidative modification of BOF slag was in-situ observed by ultra-high-temperature confocal scanning laser microscope, and the phase transformation and mineral structure evolution were analyzed by chemical analysis, X-ray diffraction and field emission scanning electron microscopy. The results demonstrated that the increase of oxidation temperature effectively promoted the transformation of iron oxides to (Mg,Fe2+)O·Fe2O3, but too high temperature could lead to the increase of iron-containing melilite phase and reduce the iron recovery. In the oxidative modification process, the appropriate holding time and cooling mode facilitated the growth and development of (Mg,Fe2+)O·Fe2O3 particles, which was conducive to the separation and recovery of iron resources. After BOF slag was oxidized at 1300 ℃ for 240 min and cooled in the furnace (1 ℃/min), the grade of magnetic slag obtained by magnetic separation had a grade of 40.26%, a recovery of 70.95%, and a P and S content of 0.042 and 0.456, respectively, which may be used as an important supplement to the raw materials for sintering. The regulated secondary slag may be used to diversify into higher value-added production. Therefore, the systematic research and development of oxidative modification-crushing-magnetic separation technology may promote the efficient utilization of BOF slag components and heat energy.

Impacts of coexisting mineral on crystallinity and stability of Fe(II) oxidation products: Implications for neutralization treatment of acid mine drainage.

The neutralization treatment of acid mine drainage involves the oxidation of Fe(II), but little is known about the effects of co-existing minerals on the oxidation and hydrolysis of Fe(II) to iron oxides. Here we investigated the transformation of fresh and heated Fe(II) oxidation coprecipitates, which were synthesized in the presence and the absence of five co-existing minerals (montmorillonite, kaolin, quartz (SiO2), aluminium oxide (Al2O3) and calcium carbonate (CaCO3)). In the FeSO4 system with montmorillonite or kaolin, the formation of lepidocrocite was inhibited with the increase of clay mineral contents. In the same system, heated coprecipitates of montmorillonite were mainly comprised of amorphous ferrihydrite and its transformation was retarded by the excess montmorillonite. In the FeCl2 system with SiO2, Al2O3 or CaCO3, akaganeite formation was inhibited with the increase in the corresponding mineral contents. In the same system, goethite formation was blocked by either CaCO3 or Al2O3 and the growth of lepidocrocite was inhibited by CaCO3 or SiO2. However, magnetite formation was enhanced by addition of CaCO3. These findings are important for predicting products of abiotic Fe(II) oxidation during the neutralization of acid mine drainage and for better understanding the transformation of amorphous iron oxides in the complicated environmental matrix.

Oxidation and phase transfer of individual Cr-doped dendritic FeOx particles visualized by full-field nano-XAFS spectroimaging.

Iron oxides with various compositions and polymorphs have been widely used as compounds that require reversible redox properties, such as catalysts. However, partial decomposition during phase transitions often causes irreversible degradation of the redox properties of iron oxides. Cr doping into the crystalline framework of iron oxide dendrites improves the stability of the structural transformation of iron oxides. We spatially visualized the FeOx-dendrite phase distribution during oxidation in crystalline dendritic FeOx and Cr-FeOx particles by full-field nano-X-ray absorption fine structure spectroimaging. The spectroimaging visualized propagation in the phase transitions in the individual FeOx particles and changes in the phase transition behaviors of the Cr-FeOx particles. The statistical analysis of the spectroimaging data revealed the phase transition trends in parts of the FeOx and Cr-FeOx particles in three Fe density zones (particle thicknesses) and the probability densities of the phase proportions in the dendrites.

Minerals phase transformation by hydrogen reduction technology: A new approach to recycle iron from refractory limonite for reducing carbon emissions

Limonite is a potentially vital iron ore resource, but it is hard to be effectively utilized by conventional mineral processing methods due to the high aluminum, silicon and water content. This paper proposed the phase transformation by hydrogen reduction technology to treat refractory limonite ore. The optimal conditions were determined as a roasting temperature of 500 °C, the reducing gas concentration of 20 % (H2:CO = 3:1), roasting time of 25 min, grinding fineness of 85 % passing 0.038 mm, the magnetic field strength of 187.5 kA/m. Under the above conditions, the concentrate with an iron grade of 59.85 % and recovery of 98.47 % was obtained. X-ray diffraction, iron chemical phase analysis and Vibrating Sample Magnetometer showed that the phase transformation of iron oxide was goethite/hematite → magnetite. Thus, the magnetism was significantly enhanced, which was conducive to magnetic separation. Electron Probe Micro Analysis indicated that it was difficult to further improve the quality of iron concentrate due to the existence of aluminum in the form of extremely fine minerals and the isomorphic replacement between aluminum and iron.

Oxidative and pyrolytic decomposition of an evaporated stream of 2,4,6-tribromophenol over hematite: A prevailing scenario during thermal recycling of e-waste

Brominated flame retardants (BFRs) constitute a major load in the polymeric fraction of e-waste. Degradation of BFRs-laden plastics over transition metal oxides is currently deployed as a mainstream strategy in the disposal and treatment of the non-metallic segment of e-waste. However, interaction of pyrolysis’s products of BFRs with transition metal oxides is well-known to facilitate the formation of notorious pollutants. Despite recent progress to comprehend the germane chemistry of this interaction, several important pertinent aspects remain to be addressed. To fill in this gap, an integrated experimental and simulation account of the pyrolytic and oxidative decomposition of a gaseous stream of 2,4,6-tribromophenol (TBP) over hematite (Fe2O3) has been reported herein. TBP is utilized as a model compounds of BFRs as their most common formulations include brominated phenolic rings. Overall, hematite entails a rather low cracking capacity under pyrolytic conditions. Analysis of condensate products indicates that oxidative degradation of a gaseous stream of TBP results mainly in the formation of brominated alkanes such as bromoethane and bromo-pentane. Likewise, Ion chromatography (IC) measurements disclosed a noticeable reduction in the concentrations of escaped HBr. Transformation of iron oxides into iron bromides (possibly in the form of FeBr2) during pyrolysis and combustion operations is evident through XRD measurements. Density functional theory (DFT) calculations map out important reactions pathways that operate in the initial degradation of the TBP molecule. From a broader perspective, outlined results shall be instrumental to precisely assess the effectiveness of using iron oxides in thermal catalytic recycling of e-waste and the likely emission of brominated toxicants.

Potential impact of dispersion products of magnetite quartzites on the environment

Using XRF, TG-DTA, chemical and sedimentation analysis of the products of processing of magnetite quartzites from the N Ore Processing Plant of Krivorozhye, changes in the phase and chemical composition of samples of four stages of magnetic separation and tailings were traced compared to a sample of the raw ore, and the potential impact of the dispersion process on the environment was revealed. Thermogravimetric studies indicate phase transformations of magnetite to maghemite (250-340 ° C), polymorphic transformations of iron oxides and destruction of rock-forming minerals (430-480 ° C), conversion of alpha quartz to beta-form (564-568 ° C), dehydroxylation of iron and magnesium oxyhydroxides (385 ° C), conversion of beta-quartz to beta-cristobalite (970 ° C). In the process of enrichment, there is an increase in the loss of mass of the samples, which is %: 0.06 (I); 1.46 (II); 1.9 (III), and 2.6 (IV). According to X-ray diffraction, the main ore mineral is magnetite, the rock-forming mineral is quartz. Among the secondary minerals are sulfides, cummingtonite, actinolite, and others. It is shown that at the first stage of enrichment all primary and secondary minerals are present in the samples, at the 2nd stage sulfides disappear from the sample, at the 3rd stage secondary minerals disappear, and at the 4th stage quartz remains in the sample and it forms aggregates with magnetite. The parameter of the crystal lattice of magnetite varies between 8.397-8.403 nm, its coherent scattering region (CSR) is 31.4-35.6 nm. It is found that in the course of ore grinding the destruction of secondary minerals takes place with the removal of destruction products, as evidenced by the occurrence of disperse quartz in the tailings. According to sedimentation analysis data, in the first 20 seconds, more than half of the particles with a size of 24-28 μm were deposited from the pulp, after 3 minutes, particles with a size of 8-9 μm settled, after 6 minutes - particles with a size of 6-7 μm. Within 30 minutes, almost complete precipitation of particles with sizes of 4.5-2.7 μm was observed. Hydraulic classification of the tailings showed the deposition of mainly quartz particles in the first and second chambers of the separator, actinolite and muscovite particles were separated in the third chamber, and cummingtonite, biotite and chlorite in the fourth chamber. Analysis of the chemical composition of the dispersion products indicates that Si, Ca, and Na accumulate in the tailings, whereas Ti is removed, and could potentially enter the environment. It is shown that the tailings and separation products increase the content of Zn, and the tailings accumulate environmentally hazardous As, and Nb. At the same time, the concentrations of other elements remain stable at all stages of processing.

A model towards understanding stabilities and crystallization pathways of iron (oxyhydr)oxides in redox-dynamic environments

Crystallization and transformation of iron (oxyhydr)oxides occur widely in redox-dynamic environments, which are closely linked to iron cycling, (im)mobilization of co-associated elements, and microbial iron metabolisms. Although numerous studies have been conducted to investigate the occurrence and fate of iron (oxyhydr)oxides under various redox conditions, the mechanism controlling these processes is still incompletely understood. Here, we present a theoretical model, based on Classical Nucleation Theory (CNT), that can be used to predict and rationalize phase-selection and crystallization pathways of iron (oxyhydr)oxides under different redox conditions. By calculating the energy landscapes of dissolved or solid-phase iron species in a Fe-H2O system as a function of Eh, pH, and particle size, we show how the stability regions of iron (oxyhydr)oxides change with geochemical environments (pH and redox potential) and initial properties of precursors (particle size and crystallinity). Through the calculation of thermodynamic driving forces and energy barriers for the nucleation of different metastable phases, the crystallization pathways of iron (oxyhydr)oxides via hydrolysis of Fe3+(aq), oxidation of Fe2+(aq), and Fe(II)-catalyzed ferrihydrite transformation can be predicted. The computational results show good agreement with previously reported experimental data. This study provides a unified model to predict and understand relative stability, transformation, and persistence of iron (oxyhydr)oxides under varying pH and redox conditions in natural environments.

Arsenic speciation transformation in soils with high geological background: New insights from the governing role of Fe.

In soils, the speciation transformation of As were inherently related to the behaviors of iron (oxyhydr) oxides. It is poorly understood that the effects of the transformation of iron (oxyhydr) oxides coupled with As speciation transformation during dissimilatory Fe(III) reduction (DIR) involving with humic substances (HS) as electron donor or shuttle in soils with high arsenic geological background. In this study, the relationships between the transformation of iron (oxyhydr)oxides and As speciation transformation were investigated according to the response between continuously As speciation monitoring and iron (oxyhydr) oxides identification during DIR in the soils. The results showed that F4 (arsenic incorporated with amorphous iron (oxyhydr)oxides including ferrihydrite and schwertmannite) and F5 (arsenic incorporated with crystalline iron (oxyhydr)oxides including hematite and magnetite) were the main source and sink for As(III)Dissolved during DIR. During the incubation period, Fe(II) was the dominant driving force for the reduction of As(V) in the water-soil system. The XRD analysis indicated the changes of iron oxides such as ferrihydrite, schwertmannite, hematite and magnetite were closely related to the release and reduction of As, and those iron oxides could play governing roles for As speciation transformation during DIR in soils. Different from the known mechanism in low As concentrations, a limiting effect of As concentration on iron oxides transformation was found in our incubation experiments using soils with high As geological background (∼1000mg/kg). This work provides new insights for Fe as governing role in As speciation transformation in soils with high arsenic geological background by firstly identifying the corresponding iron (oxyhydr)oxides in operationally defined arsenic speciation incorporated with iron oxides.

Strain-Enhanced Phase Transformation of Iron Oxide for Higher Alcohol Production from CO2

Conversion of CO2 to higher alcohols (HAs) and higher hydrocarbons (HCs) has a greater advantage compared to C1 products because of their high energy density and wide range of applications in daily life. Despite the immense potential of these chemicals, not much of scientific research has been focused on the conversion of CO2 to HAs. In the present work, we have introduced the concept of strain in designing the material to enhance the CO2 to HA performance. We introduced strain in a traditional iron-based catalyst, Fe2O3, by the introduction of indium (In), which facilitates the selective conversion of CO2 to HA. An optimum strain favored a 36.7% CO2 conversion with a 42% HA selectivity, and a record yield of 15.42%. The strain has been tuned further with the introduction of K as a promoter. The introduced strain upon In substitution and K promotion favored the conversion of CO2, which is mapped by powder X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Further, the change in the mechanism upon In incorporation and K promotion has been probed by in situ diffuse reflectance infrared fourier transform spectroscopy, and it is found that the OCHx intermediate, which produces HAs, is more prominent upon In substitution, which favored the enhancement of HA production compared to that of pristine Fe2O3.