Search Results (104)

Fe-oxyhydroxides can incorporate toxic metals during the formation of mineral phases in soils and sediments, thereby potentially altering the environmental reactivity of metals and impacting the microbial communities. In this study, isothermal microcalorimetry has been used to monitor the metabolic activity of Pseudomonas putida KT2440 exposed to pure ferrihydrite and to Pb-, Cd-, and As-bearing ferrihydrites under oxygen-limited conditions. Calorimetric measurements of the integral heat released during the exponential growth were combined with the analysis of dissolved iron and heavy metals, as well as the glucose uptake, to understand how heavy metal incorporation modifies mineral reactivity and microbial heat output. Pure ferrihydrite decreased the integral heat by about 45%, primarily due to glucose and phosphate depletion, Fe(III) leaching, and mineral–cell aggregation. Heavy metal dopants were found to modulate nutrient availability, surface charge, and Fe solubilization, which, in turn, influenced the integral heat. Pb-Fh generated the highest ferrihydrite dissolution and metabolic heat, with a maximum effect at intermediate substitution levels. As-Fh induced moderate Fe release and metabolic activity, consistent with the enhanced phosphate sorption and lowered surface charge. Cd-bearing Fh showed minimal reactivity and yielded the lowest heat output. Microcalorimetry was proven useful for unraveling microbe–mineral interactions in complex contaminated environments. Full article

Arsenic (As) contamination threatens ecosystems and human health, and iron (hydr)oxides-mediated formation of Fe-As composites is a key strategy for arsenic immobilization, while the long-term stability of these composites under complex environmental conditions remains a critical concern. This study systematically investigated the interactive effects of environmental factors (temperature: 5–35 °C, pH: 4–8, competing ions: phosphate and citrate) and material intrinsic properties (ferrihydrite aging: 0–60 days, Fe/As molar ratio: 1.875 and 5.66, adsorption time) on Fe-As composite stability using multiscale characterization techniques and theoretical modeling. Results showed that temperature was the dominant controlling factor, with arsenic release increasing by 4.25% per 1 °C rise (178% higher at 35 °C vs. 20 °C) and an exponential relationship model established (R² = 0.96). Ferrihydrite aging enhanced stability, as 60-day aged composites (Fh_60d-As) exhibited minimal arsenic release (18.83%) at pH 4/20 °C, attributed to increase As(V)-O-Fe binding energy (1.2 eV) and -OH group enhancement (12.5%). Phosphate induced 2.4-fold higher arsenic release than citrate, and lower pH (4–6) reduced release via enhanced protonation. A stability prediction model was developed (R² = 0.91), and practical remediation strategies were proposed: maintaining temperatures below 25 °C in arsenic-containing waste repositories and using pre-aged iron-based materials. This work provides quantitative benchmarks and mechanistic insights for contaminated site rehabilitation. Full article

In the early Paleoproterozoic, the Earth’s atmosphere–ocean system shifted from a reducing to an oxidizing state, triggering the extensive deposition of banded iron formations (BIFs) in the Siderian period (2.5–2.3 Ga). As a key sedimentary formed during the hydrospheric oxidation stage, BIFs are expected to preserve abundant microbial fossils or organic carbon. However, evidence for contemporaneous widespread biological activity remains limited. This paper focuses on C-O isotopes and the trace element geochemistry of the 2.5 Ga Jining BIF to constrain the redox state of paleo-oceans and associated biogeochemical cycling during BIF deposition. The δ¹³C_carb values of the BIF samples range from −18.6‰ to −9.6‰, with an average of −12.7‰, exhibiting a notable negative value, and TOC contents (0.04–0.19 wt.%) are extremely low. This suggests the incorporation of oxidized organic carbon to pore water via ferrihydrite reduction during early diagenesis process. The globally negative δ¹³C_carb value of BIFs and iron-rich carbonates reflect enhanced biological activity at ~2.5 Ga. REE patterns reveal negative Ce/Ce*_(SN) and Eu/Eu*_(CN) anomalies, and the presence of primary hematite mesobands together indicate that the Jining BIF records a redox transition in seawater from reducing to oxidizing conditions. Full article

Polyextremophilic microbial communities of Baikal Rift Zone hot springs have been studied fragmentarily, and these studies have typically focused on either phototrophic microbial mats or on the whole microbial community from one or a few sites. In our work, we conducted the first large-scale screening of microbial communities from seven hot spring groups in the Baikal Rift Zone, using metabarcoding of the V3-V4 regions of the 16S rRNA gene. Analysis of alpha and beta diversity, as well as co-occurrence network analysis, revealed that the microbial diversity of the studied springs is highly dependent on temperature values. This approach allowed classifying microbial communities into four distinct groups, characterized by significantly different taxa representing the key functional roles of primary producers, heterotrophic consumers, and terminal destructors of organic matter. Sulfate-reducing bacteria constituted a major metabolic group driving the final stage of organic matter mineralization. Moreover, the presence of alkalithermophilic dissimilatory iron reducers, whose existence was debatable, was proved in the studied samples by cultural methods. The phylotypes that gained an advantage on selective media with synthesized ferrihydrite and hydrogen or acetate added as an electron donor belonged to the genus Parvivirga of the order Anaerosomatales and several unknown representatives of the phylum Bacillota. Full article

The redox activity of natural organic matter (NOM) is crucial for contaminants transformation in soils. Soil micropores (<2.5 nm) have limited accessibility for microorganisms and large NOM molecules; therefore, insoluble organic pollutants and heavy metals trapped in these micropores are usually reached by low molecular weight fractions (LMWF) of NOM. However, the mechanism of spatial electron transfer via electron shuttle of LMWF remains unclear. In this study, we separated low molecular weight fractions (LMWF < 3500 Da and LMWF < 14,000 Da) of Leonardite humic acids (LHA) and measured its acceleration of microbial ferrihydrite reduction. The results show that LMWF, as an electron shuttle, significantly accelerates the reduction in Fe (III), among which 3500-LMWF is the main fraction contributing to the acceleration. Additionally, 3D-EEM shows that quinone content was positively correlated with reduction efficiency, supporting its role as the key functional group. Based on the accelerating experiments, we determined an electron shuttling critical distance of 117.2 nm for LMWF LHA. These findings establish LMWFs as effective natural electron shuttles, providing a theoretical basis for understanding pollutant dynamics in soil micropores. Full article

The migration of the long-lived isotope technetium-99 (half-life 2.1 × 10⁵ years) presents a significant challenge for the deep geological disposal of radioactive waste. This study investigates the immobilization of technetium by carbon steel corrosion products under aerobic and anaerobic conditions simulating the Yeniseysky site (Krasnoyarsk Region, Russia), a proposed location for a Deep Geological Repository (DGR). Over time, the degradation of barrier materials is expected to allow low-salinity solutions to be brought into contact St3 steel, the intended container material for vitrified radioactive waste in the Russian context, leading to crevice corrosion. The findings demonstrate that carbon steel containers act not merely as a physical barrier but also as a chemical barrier by facilitating the reductive immobilization of technetium. The most effective reduction of technetium was observed in the presence of ferrihydrite as a corrosion product under both aerobic and anaerobic conditions, as indicated by distribution coefficient (K_d) values ranging from 1.4 × 10³ to 1.6 × 10³ cm³/g. However, the presence of bentonite clay can diminish the efficiency of this process by adsorbing corrosion products, resulting in a 50% reduction in the distribution coefficients. In contrast, leaching products from aluminophosphate glass and cement had a less pronounced effect on technetium immobilization, causing a decrease in distribution coefficients of no more than 30%. The results of this research can be applied to model the long-term behavior of technetium in the evolving environment of a geological radioactive waste repository. Full article

Phosphate pollution caused by human activities has become a pressing environmental issue, leading to eutrophication and severe ecological risks. In this study, artificial humic acid (HA) and fulvic acid (FA) were synthesized from tung fruit and glucose, respectively, and further composited with ferrihydrite (Fh) to prepare HA/Fh and FA/Fh adsorbents for phosphate removal. The structural and morphological characteristics of the composites were confirmed by SEM, XRD, FTIR, and XPS analyses, which indicated successful complexation of HA or FA with Fh through ligand exchange and surface interactions. Batch adsorption experiments revealed that HA/Fh and FA/Fh exhibited significantly enhanced adsorption capacities compared to pristine Fh, with maximum Langmuir adsorption capacities of 33.67 mg g⁻¹ and 37.06 mg g⁻¹, respectively. The adsorption behavior was well described by the pseudo-second-order kinetic model and the Langmuir isotherm, suggesting a chemisorption-dominated process involving ligand exchange between surface –OH groups of Fh and phosphate ions, supplemented by electrostatic attraction. Coexisting ion studies demonstrated that Cl⁻ and SO₄²⁻ slightly promoted phosphate adsorption, while NO₃⁻ and CO₃²⁻ strongly inhibited it, highlighting the competition of multivalent anions with phosphate for Fe³⁺ active sites. Importantly, the phosphate-enriched adsorbents can be directly recycled as phosphorus fertilizers, providing a sustainable pathway for both environmental remediation and phosphorus resource recovery. Full article

Iron deficiency anemia (IDA) remains a global health challenge. This study pioneers the use of humic substances (HS) as natural, biocompatible macroligands to develop safer and more effective nanoferrotherapeutics. We synthesized a series of nanoscale Fe(III) oxyhydroxide complexes stabilized by different HS, employing various solvents (ethanol, isopropanol, and acetone) and precipitation methods to isolate fractions with optimized properties. The nanocomposites were comprehensively characterized using inductively coupled plasma atomic emission spectrometry, total organic carbon analysis, X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy. Cytotoxicity and iron bioavailability of all HS-Fe(III) formulations were assessed in Caco-2 intestinal epithelial cells. The type of HS and precipitation conditions significantly influenced the nanocomposites’ properties, yielding spherical nanoparticles (1–2 nm) of ferrihydrite or goethite. Physicochemical analysis confirmed that solvent-driven fractionation effectively tailored the nanocomposites’ size, crystallinity, and elemental composition. All HS-Fe(III) formulations demonstrated exceptional cytocompatibility, starkly contrasting the significant cytotoxicity of the reference drug Ferrum Lek^®. Several complexes, particularly CHSFe-Et67, surpassed Ferrum Lek^® in cellular iron uptake efficiency. We conclude that HS are a highly promising platform for developing effective and safe iron-delivery nanoferrotherapeutics, leveraging their natural polyfunctionality to enhance bioavailability and mitigate toxicity. Full article

Iron(III) (Fe(III)) complexes have recently emerged as safer alternatives to magnetic resonance imaging (MRI) contrast agents (CAs), reigniting interest in biomedical research. Although gadolinium Gd(III)-based contrast agents (CAs) have been widely used in MRI over the past four decades, their use in the current clinical routine is severely constrained due to concerns about high toxicity and environmental impact. Research is now focusing on synthesizing safer contrast agents with alternative paramagnetic ions like Fe(III) or Mn(II). MRI CAs with integrated potent therapeutic moieties may offer synergistic advantages over traditional contrast agents in clinical use. The study explored the use of salinomycin-ferrihydrite composites as possible effective ensembles of imaging and therapeutic units in the same molecule, evaluating their anticancer activity and influence on the signal in MRI. The composites were characterized using Mössbauer spectroscopy and ICP-MS for iron content determination. The in vitro relaxivity measurements in a high-field MR scanner demonstrated the potency of the composites as T₂ enhancers. The antitumor activity of one selected Sal-ferrihydrite composite was tested in three human cancer cell lines: A549 (non-small cell lung cancer); SW480 (colon cancer); and CH1/PA1 (ovarian teratocarcinoma) by the MTT cell viability assay. The new Sal-ferrihydrite composite showed a pronounced cytotoxicity in all three human cancers in line with enhanced signal in MRI, which makes it a promising candidate for future biomedical applications. The superior cytotoxic effect, together with the strong signal enhancement, makes these compounds promising candidates for further detailed investigations as future theranostic agents. Full article

Taxco de Alarcón (Mexico) has been affected by mining activities and the presence of potentially toxic elements (PTEs). In this study, water samples from the Acamixtla, Taxco, and San Juan rivers were analyzed using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) to determine PTE concentrations. Statistical analyses included principal component analysis, Pearson’s correlation, the Pollution Index, and a Health Risk Assessment. Additionally, solid samples from the San Juan River with leachate from the “La Guadalupana” Mine (RSJMG S2.3) were characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). Identified PTEs included As, Cr, Ni, Zn, Fe, Mn, Cu, Cd, Pb, Se, and Li. Principal component analysis explained 94.8% of the data variance, and Pearson’s correlation revealed significant associations (p < 0.05) among Fe, As, Cu, Cd, Pb, and Zn. The RSJMG S2.3 site exhibited the highest Pollution Index value (8491.56) and the highest health exposure risks. Lower contamination levels at other sites may be attributed to the complexation of PTEs with ferrihydrite, which was identified in the RSJMG S2.3 site through microscopy and infrared analyses. These findings suggest that the in situ formation of ferrihydrite may enhance the adsorption of PTEs, thereby mitigating environmental contamination and potential health risks. Full article

The bioavailability of heavy metals is profoundly influenced by their interactions with active soil components (microorganisms, organic matter, and iron minerals). However, the effects of urease-producing bacteria combined with organo-Fe hydroxide coprecipitates (OFCs) on Cd accumulation in wheat, as well as the mechanisms underlying these effects, remain unclear. In this study, pot experiments integrated with high-throughput sequencing were employed to investigate the impacts of the urease-producing bacterial strain TJ6, ferrihydrite (Fh), and OFCs on Cd enrichment in wheat grains, alongside the underlying soil–microbial mechanisms. The results demonstrate that the strain TJ6-Fh/OFC consortium significantly (p < 0.05) reduced (50.1–66.7%) the bioavailable Cd content in rhizosphere soil while increasing residual Cd fractions, thereby decreasing (77.4%) Cd accumulation in grains. The combined amendments elevated rhizosphere pH (7.35), iron oxide content, and electrical conductivity while reducing (14.5–21.1%) dissolved organic carbon levels. These changes enhanced soil-colloid-mediated Cd immobilization and reduced Cd mobility. Notably, the NH₄⁺ content and NH₄⁺/NO₃⁻ ratio were significantly (p < 0.05) increased, attributed to the ureolytic activity of TJ6, which concurrently alkalinized the soil and inhibited Cd uptake via competitive ion channel interactions. Furthermore, the relative abundance of functional bacterial taxa (Proteobacteria, Gemmatimonadota, Enterobacter, Rhodanobacter, Massilia, Nocardioides, and Arthrobacter) was markedly increased in the rhizosphere soil. These microbes exhibited enhanced abilities to produce extracellular polymeric substances, induce phosphate precipitation, facilitate biosorption, and promote nutrient (C/N) cycling, synergizing with the amendments to immobilize Cd. This study for the first time analyzed the effect and soil science mechanism of urease-producing bacteria combined with OFCs in blocking wheat’s absorption of Cd. Moreover, this study provides foundational insights and a practical framework for the remediation of Cd-contaminated wheat fields through microbial–organic–mineral collaborative strategies. Full article

In this research work, a natural sample from an Omani magnetite (MG) deposit was used for the synthesis of a magnetite decorated with ferrihydrite (MG-Fh), and two lanthanum (La)-modified materials at mass percentages of 5% (MG-Fh-La-5) and 15% (MG-Fh-La-15). These materials were first characterized using various analytical techniques. Then, their phosphorus (P) recovery efficacy from aqueous solutions was studied in batch mode under a wide range of experimental conditions. The characterization results show that compared to the raw feedstock, MG-Fh, MG-Fh-La-5, and especially MG-Fh-La-15 have improved structural, textural, and surface chemistry properties. Adsorption tests indicate that due to the deposition of high contents of lanthanum oxides on its surface, the MG-La-15 exhibited a large P uptake capacity (34.5 mg g⁻¹), which is significantly superior to those determined for MG-La-5 (24.3 mg g⁻¹), MG-Fh (12.4 mg g⁻¹), and various engineered materials published in the literature. Moreover, these materials retain an interesting ability to recover P from real wastewater with a highest adsorbed mass of 27.3 mg g⁻¹, observed for MG-La-15. The P recovery seems to involve both physical and chemical mechanisms, including electrostatic interactions and complexation. This research work shows that La-modified magnetite can be considered a promising and eco-friendly material for P recovery from liquid effluents. Full article

The Carajás Mineral Province hosts one of the world’s most extensive sulfide-bearing copper belts. These deposits are typically covered by thick regolith, including gossans, laterites, colluviums, and soil, which can be used as important exploration indicators. In some cases, these covers can be mined alongside the parent hypogene ore. Therefore, accurate identification of copper-bearing minerals is essential for selecting the most appropriate metallurgical techniques. This study investigated the saprolite horizon overlying the Alvo 118 deposit, where the parent rocks are chloritites hosting copper-bearing hypogene sulfides, partially altered to an immature gossan. Saprolite formation was primarily controlled by the weathering of chlorite, mostly converted into kaolinite, with smectite and vermiculite serving as intermediates, forming a typical lower saprolite association. During weathering, iron released from chlorite and indirectly by vermiculite and smectite contributed to the formation of ferrihydrite, goethite, and hematite. Magnetite octahedrons, relics of the hypogene ore, pseudomorphic phases, are embedded in the clay mineral matrix. While FTIR analysis of kaolinite showed no evidence of copper retention, Mössbauer spectroscopy enabled the quantification of iron-bearing minerals, revealing a strong correlation between CuO contents and goethite and ferrihydrite. These results suggest that goethite and ferrihydrite may be the main copper carriers in the deposit, consistent with findings from similar deposits. Weak acid leaching is proposed as the most effective technique for copper extraction from this mineralization type. Full article

Limited methods exist to determine the composition of particle mixtures. This research presents a simple UV-vis-spectroscopy-based method for the separate quantification of particles mixtures considering the following: synthesized ferrihydrite, commercial Fe₂O₃, and natural allophane. Calibration curves and adsorption/scattering coefficients are determined for each particle at different wavelengths. This is the main input to solve equation systems and, ultimately, quantify particle concentration in binary mixtures. The limit of detection varies with wavelength and particle type, yielding values as low as 1.5, 0.2, and 1.6 mg L⁻¹ for ferrihydrite (500 nm), Fe₂O₃ (450 nm), and natural allophane (450 nm), respectively. This study provides a simple, low-cost and straightforward method, compared to atomic-spectroscopy- or chromatography-based techniques, for resolving the composition of binary particle mixtures in suspension. Full article

Through the analysis of core-rim magnetite, we demonstrate that the core contains carbonaceous materials (CMs) derived from a 3.2-billion-year-old banded iron formation within the Barberton Greenstone Belt in South Africa. Using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy, we establish a direct association between these CMs and the magnetite. Although the possibility that CMs formed from the hydrothermal decomposition of siderite cannot be ruled out, several lines of evidence indicate a likely microbial origin for the CMs. Firstly, Raman spectroscopy reveals that the CMs exhibit characteristics of low-maturity biogenic organic matter (OM) featuring aliphatic carbon chains, which supports the notion that organic carbon compounds mature during burial metamorphism at temperatures below approximately 200 °C. Secondly, phosphorus and sulfur detected in the CMs suggest a microbial origin. Lastly, the formation of the unique texture of core-rim magnetite can be conceptualized as follows: Fe²⁺ is oxidized through anoxygenic photosynthesis, leading to the precipitation of ferrihydrite. This ferrihydrite is then transformed into magnetite by iron-reducing microorganisms. Subsequently, the magnetite grows larger through oriented attachment, which also confines OM. Ultimately, smooth magnetite rims may have preserved the OM for up to 3.2 billion years. Full article