Secondary Iron Research Articles

The Influence of the Assembly Unit of CO2-Cured Secondary Aluminum Ash and CO2-Cured Iron Tailings on High Performance Concrete’s Properties

This paper aims to study the influence of the assembly units of CO2-cured iron tailings (IOT) and CO2-cured secondary aluminum ash (SAA) on the fresh high-performance concrete’s (HPC’s) slump flow and setting time. The mechanical properties including the flexural strength, compressive strength, the bonding strength and the dry shrinkage rate of the hardened HPC are measured. The amount of leached Cr and Zn after immersing in deionized water for 1 month~6 months is measured. The influence of the basalt fibers’ volume ratio and the aspect ratio of the high-performance concrete’s performance is considered. The scanning electron microscopy energy spectrums (SEM-EDS) are obtained. The results show that the slump flow and the setting time of fresh HPC are increased by the added CO2-cured SAA and IOT. The fresh HPC with 10% CO2-cured IOT and 20% CO2-cured SAA had the highest slump flow. The slump flow decreases in the form of cubic function with the placing time. The mechanical strengths and the dry shrinkage rate of HPC during the early curing ages (cured for 0.5 day~7 days) are decreased by the CO2-cured SAA and CO2-cured IOT, while the mechanical strengths at later curing ages (14 days~90 days) are increased by the added CO2-cured SAA and CO2-cured IOT. HPC with 10% CO2-cured SAA and 20% CO2-cured IOT shows the highest mechanical strengths. The amount of leached Cr and Zn is decreased by the CO2 cured SAA and IOT. The relationship between the mechanical strengths and the curing time coincides with the cubic equation. The basalt fibers with a volume ratio of 2% and aspect ratio of 1000 show the highest mechanical strengths, the lowest dry shrinkage rate and the least amount of leached Cr and Zn. CO2-cured SAA and IOT can improve the compactness of HPC’s hydration products. HPC with 10% CO2-cured SAA and 20% CO2-cured IOT shows the highest compact hydration products.

Sugarcane bagasse and iron ore tailings thermochemical conversion towards sustainable iron recovery with biogenic carbon and hydrogen production

The recovery of valuable chemical elements from industrial waste is essential for production processes' economic and environmental sustainability. The interaction between the iron ore tailings and sugarcane bagasse, both wastes, has the potential to provide a secondary iron source for future iron and steelmaking processes. This study evaluated the use of volatiles from sugarcane bagasse (SCB) and iron ore tailings (IOT) to the synergistic promotion of carbon deposition, H2 production and conversion of weak magnetic iron oxides in strong magnetic iron phases. The experiments were carried out at 400, 600, 800, and 1000 ºC with different SCB/IOT ratios under an N2 atmosphere. In all tests, SCB and IOT were heated simultaneously in separate beds to prevent direct contact between the materials. The combination of 600 ºC and higher SCB/IOT ratio resulted in a product with 96.7% magnetite, 98% magnetic fraction recovery, and 3.5% deposited carbon. The use of lower SCB/IOT ratio provided an increase in H2 production. Regardless of the mass ratio, heating the IOT and SCB simultaneously up to 1000 ºC led to significant mineralogical transformations, reaching reduced phases such as wüstite, fayalite and metallic iron, which impaired magnetic separation efficiency. The results indicate an alternative for recovering iron from IOT using biomass waste as a renewable reducing agent for the steel industry.

Recurrent BMP4 variants in exon 4 cause non-HFE-associated hemochromatosis via the BMP/SMAD signaling pathway

BackgroundHereditary hemochromatosis (HH) is an iron overload disorder and can be caused by variants in non-HFE genes in Chinese patients. However, there is still a considerable proportion of patients suffering from unexplained iron overload. In our previous study, we had identified the p.R269Q variant in exon 4 of the Bone morphogenetic protein 4 (BMP4) gene in Chinese patients with unexplained primary iron overload by Whole Exome sequencing, and then the BMP4 p.H251Y variant was identified by Sanger sequencing in a Chinese patient with secondary iron overload. Our study aimed to explore the pathogenicity and underlying mechanism of BMP4 p.H251Y and BMP4 p.R269Q variants in patients with iron overload.MethodsSanger sequencing was conducted to identify the novel variants in the BMP4 gene of patients with unexplained iron overload. MRI and liver biopsy were used to display iron overload in the liver of the patient harboring the BMP4 p.H251Y variant. The BMP4 and hepcidin levels in BMP4 knockdown and BMP4 variant cells were examined by enzyme-linked immunosorbent assay. The effects of BMP4 p.H251Y and BMP4 p.R269Q variants on the hepcidin-regulation pathway were studied.ResultsOne of 54 HH patients (1.85%) harbored the BMP4 p.R269Q variant. One of 148 patients (0.68%) with secondary hemochromatosis harbored the BMP4 p.H251Y variant, and these two variants were not found in 100 Chinese general population. For the patient harboring the BMP4 p.H251Y variant, abdominal MRI and Perl's staining of liver tissue displayed iron overload in the liver. Cells transfected with the BMP4 p.H251Y and p.R269Q variants showed down-regulation of hepcidin level and BMP/SMAD pathway compared with cells transfected with the wild-type BMP4 vector.ConclusionThe BMP4 p.H251Y and p.R269Q variants can downregulate hepcidin levels by inhibiting the BMP/SMAD axis, suggesting they may play pathogenic roles in iron overload.

Compositional and textural evidences of Na-bentonite authigenesis in the Pellegrini lake deposit (Neuquen basin, Argentina)

Textural and compositional variations of Na-bentonites from the Pellegrini Lake deposit (Neuquén Basin) have been established, with special emphasis on petrographic features in order to better understand the genetic pathways in their formation. In this region, two bentonite beds named “white bentonite” and “green bentonite” are mined mainly for the oil and foundry industries. The genesis of these beds was studied using petrological (petrography, SEM and TEM), mineralogical (DRX, FT-IR, DTA-TGA, 27Al MAS NMR) and geochemical (ICP-AES) data from two quarries named COR and CA. The bentonites mainly consist of Na-montmorillonite, with lesser amounts of quartz, plagioclase, potassium feldspar, illite, zeolite, barite and gypsum. Mineralogical and petrographical evidence indicates that the authigenic smectite was formed by devitrification of unstable glass shards in a shallow coastal marine environment. Green bentonite would be the result of several episodes of volcanic ash-fall input from multiple eruptions with a higher degree of alteration uppermost in the bed. In this case, the alteration would have occurred in a reducing environment as evidenced by the greenish colouration of these bentonites, the Ce anomaly and the presence of pyrite. Meanwhile, white bentonite would have formed in a less restricted environment than green bentonite, as evidenced by the existence of intercalations of silt-sized grains and a higher amount of detrital grains in the clay groundmass transported probably by fresher waters. The presence of celestine, barite, halite and gypsum indicates evaporitic conditions after smectite formation. The observed secondary gypsum and iron staining of surfaces are much later processes. Green bentonite samples indicate a trachyandesite composition of the parent material, while the white bentonite suggests a parent material most related to a rhyodacite/dacite composition showing that the characteristics of the volcanism might have changed with time.

Influences and mechanisms of iron input for methane productions in peatlands.

Atmospheric deposition provides a stable iron source for peatlands. The influences of Fe input on methane (CH4) productions and the underlying mechanisms remain unclear. We conducted a microcosm experiment with peat sediments collected from the Qinghai-Tibet Plateau of China to explore the effects of ferrihydrite reductionfor CH4 productions in peatlands by using geochemical analyses including 57Fe Mössbauer spectroscopy and three-dimensional fluorescence spectroscopy (3D-EEM) in combination with high-throughput sequencing of 16S rRNA and real-time fluorescence quantitative PCR (qPCR). Results showed that ferrihydrite reduction significantly increased CH4 production, being 30 times of that under the control. Selective extractions for iron oxides and 57Fe Mössbauer spectroscopy measurements revealed that no crystalline secondary iron minerals were formed during the ferrihydrite reduction process. The addition of ferrihydrite enhanced the degradation of dissolved organic matter (DOM) in peat soil, resulting in a reduction in the concentration of dissolved organic carbon (DOC). Furthermore, the relative abundance of typical fermentative microorganisms in peat sediments, including Acidobacteriota and Bacteroidota, significantly increased. Such a result indicated that reduction of ferrihydrite accelerated organic matter decomposition and increased substrate concentration required for methanogenesis. Furthermore, a co-increase in relative abundance of Geobacter, Geothrix, and Methanobacterium in the ferrihydrite-amended group suggested a potential synergistic interaction that may promote the CH4 production. Our results demonstrated that ferrihydrite reduction could significantly enhance CH4 production and play a vital role in regulating CH4 emissions in peatlands.

Effects of pH on coprecipitation of As(III) with biogenic synthesized schwertmannite and jarosite

ABSTRACT Secondary iron minerals play significant roles in the immobilization of As under acidic conditions, such as acid mine drainage. However, previous research works have not clarified the effect of pH on As(III) removal through coprecipitation with secondary minerals. Therefore, in this study, we aimed to investigate the discrepancy in As(III) coprecipitation with biogenic synthesized schwertmannite (Sch) and jarosite (Jar) at different pH values. For this, concentrations of Fe2+, TFe, S O 4 2 − , and As(III) in shake flasks were monitored during an overall incubation period of 83 h at initial pH of 1.5, 2.0, and 2.5. In addition, the physicochemical properties of collected minerals after incubation were identified using scanning electron microscopy, X-ray diffraction, pore size distribution, and Brunauer – Emmett – Teller surface area analyses. Our results showed that almost no mineral synthesis and no As(III) removal were detected in coprecipitated schwertmannite (Co-Sch) system and coprecipitated jarosite (Co-Jar) system at an initial pH of 1.5. The TFe precipitation efficiencies and As(III) removal efficiencies increased considerably and morphologies of Co-Sch and Co-Jar improved significantly when the initial pH value increased from 2.0–2.5. The maximum TFe precipitation efficiency and As(III) removal efficiency reached 30.8% and 89.6%, respectively, for the Co-Sch system, and were 47.5% and 37.4%, respectively, for the Co-Jar system. The overall results show that pH significantly affects the formation of Co-Sch and Co-Jar and the behaviour of As(III) coprecipitation.

Overlooked pyrite-mediated heterogeneous Fenton processes: Mechanisms of surface hydroxyl radical generation and associated decontamination performance

Pyrite-based Fenton-like processes have been extensively studied for wastewater decontamination; however, most relevant studies placed excessive emphasis on the homogeneous Fenton reaction mediated by aqueous Fe2+, resulting in the proposed technologies facing issues such as additional acid requirements for pH adjustment and excessive iron sludge production. Herein, through in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), custom dual-chamber reactor experiments, and a series of control experiments, significant hydroxyl radical generation was identified during the pyrite/H2O2 process, while the dominant reactive iron species was verified to the structural Fe sites on the pyrite surface, rather than structural Fe(II) in secondary iron minerals and surface adsorbed Fe2+. Consequently, even with significant suppression of the homogeneous Fenton pathway, the pyrite/H2O2 process exhibited significant degradation efficiency for sulfamethoxazole (SMX) at pH 4. Moreover, the pyrite/H2O2 process was found to selectively remove 50 μM of pollutants with high affinity for pyrite (bisphenol A, carbamazepine, nitrobenzene, and SMX), even in the presence of 50–100 mM methanol. Compared to the typical iron-based reductive catalyst (zero-valent iron, ZVI), pyrite mediated a Fenton process with greater potential for practical applications at pH 4, achieving a 43.75-fold reduction in iron sludge production and almost doubling the H2O2 utilization efficiency. Additionally, in contrast to ZVI, minimal iron oxide formed on the pyrite surface during the oxidation process. Thus, after seven cycles of degradation experiments, the decontamination efficiency of the pyrite/H2O2 process remained stable. These findings are crucial for understanding the complex environmental behavior of pyrite in both natural and engineering processes and provide a new perspective for the efficient utilization of pyrite resources as well.

Nitrate and nitrite reduction by adsorbed Fe(II) generated from ligand-promoted dissolution of biogenic iron minerals in groundwater

Chemical denitrification by redox-active Fe(II) species is pivotal in the coupled iron and nitrogen cycles. The reductive dissolution of ferric minerals by ligand can generate Fe(II)-ligand complexes, but their reducing capability for electrophilic pollutants like nitrate and nitrite remains uncertain. Here, biogenic secondary iron minerals (SIM) after dissimilatory iron reduction were reductively dissolved by oxalate and the siderophore desferrioxamine B, and subsequently the partially-dissolved SIM (SIMD) effectively removed NO2− from groundwater via reduction, while exhibiting much lower reactivity towards NO3−. The dissolution and removal processes were well-fitted with the Kabai model and the pseudo-second-order adsorption model, respectively. The equilibrium NO2− removal capacity (qe) of SIMD reached 0.146–0.223 mmol/g, accompanied with the rate constants as 0.433–0.810 g/(mmol·h). The emission of N2O and NO verified the occurrence of chemical denitrification during NO2− removal by SIMD. From the perspective of Fe(II) reactivity, SIMD exhibited higher densities of surface Fe(II) and more negative Eh values than SIM, and these two indicators showed linear correlations with the removal rates. Combined with microscopic, electrochemical and spectral analysis, our results indicated the redox reaction of adsorbed Fe(II)-complexes with NO2− on SIMD surface. The concurrent substance biochar was also considered, as it indirectly influenced dissolution and pollutant removal by shifting the iron mineral phase in SIM from magnetite to goethite. These findings highlight the significant role of reductive dissolution of iron mineral in N transformation, expand the electron pool available to support chemical denitrification, and have implications for Fe and N cycling coupling with pollutant reduction.

Uncovering Availability of the Secondary Iron Resources in China: Integrating Material Flow Analysis and Secondary Resources Reserve Assessment.

As the largest iron and steel producer, China still cannot meet its demand of iron and steel only through domestic primary supply in the last few decades. Hence, secondary iron resources are increasingly significant in meeting China's iron supply and demand balance. However, the secondary iron resource availability in China and how it impacts the future supply demand balance were still insufficiently discussed. In this work, we developed a material flow analysis and secondary resources reserve assessment (MFA-SRRA) integrated model, assessed secondary iron resources availability, and conducted a supply demand analysis through nine scenarios for irons in China. The results showed that China's secondary iron reserves will increase from 8.9 Gt in 2021 to 14.04 to 19.01 Gt in 2050. With the increasing secondary iron supply, more than 60% of iron ore as a source of steelmaking can be replaced by 2050. Landfills, as a significant reserve of iron but always ignored, will accumulate 1.42-1.51 Gt secondary iron resources by 2050 and should be noticed to be mined and utilized in the future. Last, we suggest that promoting innovation in landfill mining technology and making sustainable material management policies are urgent to prevent these secondary iron resources from becoming real waste.

Intermittent hypoxia exacerbates metabolic dysfunction-associated fatty liver disease by aggravating hepatic copper deficiency-induced ferroptosis.

Intermittent hypoxia (IH) is an independent risk factor for metabolic dysfunction-associated fatty liver disease (MAFLD). Copper deficiency can disrupt redox homeostasis, iron, and lipid metabolism. Here, we investigated whether hepatic copper deficiency plays a role in IH-associated MAFLD and explored the underlying mechanism(s). Male C57BL/6 mice were fed a western-type diet with adequate copper (CuA) or marginally deficient copper (CuD) and were exposed separately to room air (RA) or IH. Hepatic histology, plasma biomarkers, copper-iron status, and oxidative stress were assessed. An in vitro HepG2 cell lipotoxicity model and proteomic analysis were used to elucidate the specific targets involved. We observed that there were no differences in hepatic phenotypes between CuA-fed and CuD-fed mice under RA. However, in IH exposure, CuD-fed mice showed more pronounced hepatic steatosis, liver injury, and oxidative stress than CuA-fed mice. IH induced copper accumulation in the brain and heart and exacerbated hepatic copper deficiency and secondary iron deposition. In vitro, CuD-treated cells with IH exposure showed elevated levels of lipid accumulation, oxidative stress, and ferroptosis susceptibility. Proteomic analysis identified 360 upregulated and 359 downregulated differentially expressed proteins between CuA and CuD groups under IH; these proteins were mainly enriched in citrate cycle, oxidative phosphorylation, fatty acid metabolism, the peroxisome proliferator-activated receptor (PPAR)α pathway, and ferroptosis. In IH exposure, CuD significantly upregulated the ferroptosis-promoting factor arachidonyl-CoA synthetase long chain family member (ACSL)4. ACSL4 knockdown markedly eliminated CuD-induced ferroptosis and lipid accumulation in IH exposure. In conculsion, IH can lead to reduced hepatic copper reserves and secondary iron deposition, thereby inducing ferroptosis and subsequent MAFLD progression. Insufficient dietary copper may worsen IH-associated MAFLD.

Iron incorporation in red blood cells of pediatric sickle cell anemia: a stable isotope pilot investigation.

Sickle cell anemia (SCA) is marked by hypoxia, inflammation, and secondary iron overload (IO), which potentially modulate hepcidin, the pivotal hormone governing iron homeostasis. The aim was to evaluate the iron incorporation in red blood cells (RBC) in SCA pediatric patients, considering the presence or absence of IO. SCA children (n = 12; SCAtotal) ingested an oral stable iron isotope (57Fe) and iron incorporation in RBC was measured after 14 days. Patients with ≥1000 ng/mL serum ferritin were considered to present IO (SCAio+; n = 4) while the others were classified as being without IO (SCAio-; n = 8). Liver iron concentration (LIC) was determined by Magnetic Resonance Imaging (MRI) T2* method. The SCAio+ group had lower iron incorporation (mean ± SD: 0.166 ± 0.04 mg; 3.33 ± 0.757%) than SCAio- patients (0.746 ± 0.303 mg; 14.9 ± 6.05%) (p = 0.024). Hepcidin was not different between groups. Iron incorporation was inversely associated with serum ferritin level (SCAtotal group: r = -0.775, p = 0.041; SCAio- group: r = -0.982; p = 0.018) and sickle hemoglobin (HbS) presented positive correlation with iron incorporation (r = 0.991; p = 0.009) in SCAio- group. LIC was positively associated with ferritin (SCAtotal: r = 0.921; p = 0.026) and C reactive protein (SCAio+: r = 0.999; p = 0.020). SCAio+ group had lower iron incorporation in RBC than SCAio- group, suggesting that they may not need to reduce their intake of iron-rich food, as usually recommended. Conversely, a high percentage of HbS may indirectly exacerbate hypoxia and seems to increase iron incorporation in RBC. This trial was registered at www.ensaiosclinicos.gov.br . Identifier RBR-4b7v8pt.

Exploring Rare Earth Element behavior in the Mount Etna volcanic aquifers (Sicily)

This study presents the first data on REY (Rare Earth Elements plus Yttrium) in the aquifer of Mount Etna (Sicily, Italy). Patterns normalized to chondrites indicate strong water–rock interaction, facilitated by a slightly acidic pH resulting from the dissolution of magma-derived CO2. REY patterns provide insights into the processes of both mineral dissolution and the formation of secondary phases. The relative abundance of light to heavy rare earth elements is compatible with the prevailing dissolution of ferromagnesian minerals (e.g., olivine or clinopyroxenes), reinforced by its strong correlation with other proxies of mineral dissolution (e.g., Mg contents). Pronounced negative Ce anomalies and positive Y anomalies demonstrate an oxidizing environment with continuous formation of secondary iron and/or manganese oxides and hydroxides. The Y/Ho fractionation is strongly influenced by metal complexation with bicarbonate complexes, a common process in C-rich waters. In the studied system, the measured REY contents are always below the limits proposed by Sneller et al. (2000, RIVM report, Issue 601,501, p. 66) for surface water and ensure a very low daily intake from drinking water.

Sequestration of Labile Organic Matter by Secondary Fe Minerals from Chemodenitrification: Insight into Mineral Protection Mechanisms.

Labile organic matter (OM) immobilized by secondary iron (Fe) minerals from chemodenitrification may be an effective way to immobilize organic carbon (OC). However, the underlying mechanisms of coupled chemodenitrification and OC sequestration are poorly understood. Here, OM immobilization by secondary Fe minerals from chemodenitrification was investigated at different C/Fe ratios. Kinetics of Fe(II) oxidation and nitrite reduction rates decreased with increasing C/Fe ratios. Despite efficient sequestration, the immobilization efficiency of OM by secondary minerals varied with the C/Fe ratios. Higher C/Fe ratios were conducive to the formation of ferrihydrite and lepidocrocite, with defects and nanopores. Three contributions, including inner-core Fe-O and edge- and corner-shared Fe-Fe interactions, constituted the local coordination environment of mineral-organic composites. Microscopic analysis at the molecular scale uncovered that labile OM was more likely to combine with secondary minerals with poor crystallinity to enhance its stability, and OM distributed within nanopores and defects had a higher oxidation state. After chemodenitrification, high molecular weight substances and substances high in unsaturation or O/C ratios including phenols, polycyclic aromatics, and carboxylic compounds exhibited a stronger affinity to Fe minerals in the treatments with lower C/Fe ratios. Collectively, labile OM immobilization can occur during chemodenitrification. The findings on OM sequestration coupled with chemodenitrification have significant implications for understanding the long-term cycling of Fe, C, and N, providing a potential strategy for OM immobilization in anoxic soils and sediments.

Kinetics of ferrihydrite reduction in a biofilm system

Microorganisms can exist in both suspended and attached forms in natural and engineered systems. While extensive research has been performed to investigate the bioreduction kinetics of iron oxides by suspended microorganisms, the kinetics of iron oxide reduction by biofilms has not been well studied. This study investigated the rates of ferrihydrite bioreduction by biofilms of Shewanella oneidensis MR-1 with variable concentration ratios of electron donor to acceptor, and different biofilm thickness. Results indicated that the bioreduction rate of ferrihydrite by biofilms increased with increasing biofilm surface area and was faster than that by suspended microorganisms for the same biomass amount, apparently as a result of the biofilm surface area facilitating the direct contact between ferrihydrite and microorganisms for electron transfer. Increasing biofilm thickness decreased bioreduction rate for the same total biomass as a result of the decrease of the ratio of the biofilm surface area to total biomass. The bioreduction rate increased with increasing electron donor and ferrihydrite inputs, consistent with the saturation type of kinetic models. The different rates of ferrihydrite reduction in the biofilm system resulted in different rates of Fe(II) production as a function of electron donor, acceptor, and biofilm surface area, which in turn affected the type and concentrations of the secondary iron minerals, such as lepidocrocite and goethite. A kinetic model was developed that integrates biofilm surface area, and electron donor and acceptor concentrations that well described the measured rates of ferrihydrite bioreduction. The results emphasized the importance of the biofilm surface area in understanding and modeling iron redox biogeochemistry and iron-related biogeochemical processes.

Twenty years of private well testing in New Jersey: A review of the United States's most comprehensive well water testing regulation

Abstract Since the adoption of New Jersey (NJ) Private Well Testing Act (PWTA) over 20 years ago, approximately 134,000 wells have been tested, representing an estimated 34% of the private wells in NJ. The PWTA requires testing of raw water from residences with a private well at real estate transfer. Landlords are required to test private wells every five years and provide results to tenants. There are up to 43 required parameters including bacteria, volatile organic compounds (VOCs), synthetic organic compounds (SOCs), arsenic, iron, lead, mercury, nitrates, gross alpha radioactivity, uranium, three per- and polyfluoroalkyl substances (PFAS), alongside secondary contaminants iron, manganese, and pH. Among tested wells, 15.7% had at least one or more exceedance of a primary drinking water standard. The most common exceeding contaminants have historically been gross alpha radioactivity and arsenic, but since the inclusion of PFAS in 2022, over 12% of wells have exceeded for at least one PFAS. Jurisdictions interested in developing real estate private well testing policies can contemplate many of the findings, successes, and limitations of NJ's PWTA and should consider private well testing policies as a part of a larger private well program which brings together local, state, and federal resources.

Antimony isotope fractionation during Sb(V) and Sb(III) adsorption on secondary Fe-minerals (schwertmannite, ferrihydrite) typical of mine waters

The application of antimony (Sb) isotopes as tracers for Sb environmental cycling is currently limited. Indeed, there is a lack of knowledge of isotope fractionation factors associated with key (bio-) geochemical processes controlling its behaviour in surface environments. This study investigated the equilibrium isotope fractionation generated by Sb(V) and Sb(III) sorption on two iron minerals typical of acid mine drainage (AMD) impacted streams, ferrihydrite and schwertmannite, under controlled conditions of pH and solid to liquid ratio. Sorption behaviour and Sb isotope fractionation were similar for the different mineral phases and Sb oxidation degrees, with fractionation factors Δ123Sbsolid-solution of −0.25 ± 0.08 ‰ for Sb(III) and −0.34 ± 0.08 ‰ for Sb(V) adsorbed on ferrihydrite and −0.36 ± 0.06 ‰ for Sb(III) and −0.27 ± 0.03 ‰ for Sb(V) adsorbed on schwertmannite. The pH and initial Fe:Sb ratio did not significantly affect the Δ123Sbsolid-solution value under the experimental conditions. The light 121Sb isotope was preferentially adsorbed on the mineral phases, following an equilibrium closed system between dissolved and adsorbed Sb species. This fractionation may be related to the apparition of iron as the second closest neighbour which distorts the Sb(OH)3 or Sb(OH)6- atomic polyhedron. This study confirms that Sb equilibrium isotope fractionation occurs during sorption of Sb(III) and Sb(V) onto secondary iron minerals and suggests that the pH and redox of Sb do not exert significant effect. pH and redox conditions are important parameters which control Sb mobility in AMD streams, therefore, the study provides data for interpreting Sb isotope signatures in mine waters.

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.

Antimony(V) behavior during the Fe(II)-induced transformation of Sb(V)-bearing natural multicomponent secondary iron mineral under acidic conditions

Fe(II)-induced phase transformations of secondary iron minerals have attracted considerable attention due to their influence on antimony (Sb) mobility. However, Fe(II)-induced natural multicomponent secondary iron mineral (nmSIM) transformations and the corresponding repartitioning of Sb on nmSIM under acidic conditions upon Fe(II) exposure have not been systematically examined. Herein, we investigated the effect of Fe(II) on nmSIM mineralogy and Sb mobility in Sb(V)-bearing nmSIM at pH 3.8 and 5.6 at various Fe(II) concentrations over 15 d. The Sb(V)-bearing nmSIM phase transformation occurred under both strongly and weakly acidic conditions without Fe(II) exposure, while the presence of Fe(II) significantly intensified the transformation, and substantial amounts of intermediary minerals, including jarosite, ferrihydrite, lepidocrocite and fougerite, formed during the initial reaction stage, especially at pH 5.6. X-ray diffraction (XRD) analyses confirmed that goethite and hematite were the primary final-stage transformation products of Sb(V)-bearing nmSIM, regardless of Fe(II) exposure. Throughout the Sb(V)-bearing nmSIM transformation at pH 3.8, Sb release was inversely related to the Fe(II) concentration in the initial stage, and after maximum release was achieved, Sb was gradually repartitioned onto the nmSIM. No Sb repartitioning occurred in the absence of Fe(II) at pH 5.6, but the introduction of Fe(II) suppressed Sb release and improved Sb repartitioning on nmSIM. This transformation was conducive to Sb reimmobilization on Sb(V)-bearing nmSIM due to the structural incorporation of Sb into the highly crystalline goethite and hematite generated by the Sb(V)-bearing nmSIM transformation, and no reduction of Sb(V) occurred. These results imply that Fe(II) can trigger mineralogical changes in Sb(V)-bearing nmSIM and have important impacts on Sb partitioning under acidic conditions. These new insights are essential for assessing the mobility and availability of Sb in acid mine drainage areas.

Establishing a green biodesulfurization process for iron ore concentrates in stirred tank and leaching column bioreactors using Acidithiobacillus thiooxidans.

The presence of sulfur impurities in complex iron ores represents a significant challenge for the iron mining and steel-making industries as their removal often necessitates the use of hazardous chemicals and energy-intensive processes. Here, we examined the microbial and mineralogical composition of both primary and secondary iron concentrates, identifying the presence of Sulfobacillus spp. and Leptospirillum spp., while sulfur-oxidizing bacteria were absent. We also observed that these concentrates displayed up to 85% exposed pyrrhotite. These observations led us to explore the capacity of Acidithiobacillus thiooxidans to remove pyrrhotite-sulfur impurities from iron concentrates. Employing stirred tank bioreactors operating at 30°C and inoculated with 5·106 (At. thiooxidans cellsmL-1), we achieved 45.6% sulfur removal over 16days. Then, we evaluated packed leaching columns operated at 30°C, where the At. thiooxidans enriched system reached 43.5% desulfurization over 60days. Remarkably, sulfur removal increased to 80% within 21days under potassium limitation. We then compared the At. thiooxidans-mediated desulfurization process, with and without air supply, under potassium limitation, varying the initial biomass concentration in 1-m columns. Aerated systems facilitated approximately 70% sulfur removal across the entire column with minimal iron loss. In contrast, non-aerated leaching columns achieved desulfurization levels of only 6% and 26% in the lower and middle sections of the column, respectively. Collectively, we have developed an efficient, scalable biological sulfur-removal technology for processing complex iron ores, aligning with the burgeoning demand for sustainable practices in the mining industry.

An Investigation of Allyl-Substituted Bis(Diphosphine) Iron Complexes: Towards Precursors for Cooperative CO2 Activation.

In developing homogenous catalysts capable of CO2 activation, interaction with a metal center is often imperative. This work provides primary efforts towards the cooperative activation of CO2 using a Lewis acidic secondary coordination sphere (SCS) and iron via a paired theoretical/experimental approach. Specifically, this study reports efforts towards [Fe(diphosphine)2 (N2 )] as a CO2 -coordinated synthon where diphosphine=1,2-bis(di(3-cyclohexylboranyl)propylphosphino)ethane) (P2 BCy 4 ) or its precursor, 1,2-bis(diallylphosphino)ethane (tape). Initial efforts toward the {Fe(0)-N2 } complex were focused on deprotonation reactions of [Fe(diphosphine)2 (H)(NCCH3 )]+ and reduction of [Fe(tape)2 Cl2 ]. In the latter case, a mixture of intramolecularly π-bonded alkene and associated metallacyclic Fe(II)-H species were produced - heating this mixture provided the hydride as the major product. Notably, the interconversion of this pair counters that of related intermolecular reactions between [Fe(depe)2 ] (depe=1,2-bis(diethylphosphino)ethane) and ethylene, where hydride formation occurs subsequent to π-coordination; this has been probed by theoretical calculations. Finally, reactivity of the metallacyclic {Fe(II)-H} complex with CO2 was probed, resulting in a pair of isomeric ferra(II)lactones.