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Ferric hydrate has been extensively applied for the removal of various types of pollutants from wastewater because of its low cost and high efficiency. However, its wide-scale application has been greatly restricted by high-dose and low-adsorption capacity. Therefore, a novel Ca-doped ferrihydrite adsorbent has been synthesized and used for the enhanced removal of fluoride from wastewater in the presence of other co-existing ions. At 5 mg/L initial fluoride concentration and pH 5, the removal efficiency of fluoride approached to 97.5% and remained stable. Similarly, with the increase of dose from 100 to 300 mg/L, the fluoride removal linearly increased to 98% and remained plateau at neutral pH. Also, the presence of co-existing ions such as NO 3 − , SO 4 2− , Cl − , and natural organic matter has not significantly influenced the removal performance of the adsorbent. Fluoride removal best fit the pseudo-second-order reaction kinetics and Langmuir isotherm model. The prepared adsorbent exhibited a maximum adsorption capacity of 53.21 mg/g for fluoride uptake from water. The SEM-EDX confirmed the doping of Ca onto the ferrihydrite where the elemental peaks of Ca and Fe emerged at the energy value of about 3.6 Kev and 7.1 Kev respectively in EDX analysis. In addition, SEM results of Ca-doped ferrihydrite adsorbent illustrated that a large microplates type of products was acquired after synthesis. The regeneration results confirmed that adsorbent could retain their original adsorption capacity after five regeneration cycles. The current study suggested that Ca-doped ferrihydrite has the application potential for the enhanced adsorption of fluoride from the water phase. Graphical abstract

PurposeThe close association of Fe-oxyhydroxides and clay minerals might influence the sorption properties of these components. We aimed to study the effect of removing the pedogenic Fe-oxyhydroxides on the sorption of Cd, Cu, Pb, and Zn by the clay mineral particles in soils with contrasting pH.MethodsCompetitive batch sorption experiments before and after Fe-oxyhydroxide extraction in soils were carried out together with the direct analysis of the metal sorption on individual particles of ferrihydrite, smectite, and illite/smectite by TEM.ResultsFerrihydrite was a more effective metal sorbent than clay minerals, although its removal resulted in decreased sorption only for Cd, Cu, and Zn. Ferrhydrite coating blocked metals’ access for certain sorption sites on clay surfaces, which were only accessible for Pb as the most efficient competitor after removing the coating. This observation was the most remarkable for the smectite particles in the alkaline soil. Mineral surfaces sorbed higher Cu than Pb concentrations and higher Zn than Cd concentrations despite the former metals’ lower bulk sorption. Thus, organic surfaces and precipitation contributed to Pb and Cd’s retention to a greater extent than for Cu and Zn. The structural Fe of smectite also promoted the metal sorption in both soils.ConclusionRemoval of iron-oxyhydroxide coatings from the soil affects metal sorption selectively. Direct study of metal sorption on individual soil particles enables us to gain a more in-depth insight into soil minerals’ role in this process.

Metastable ferrihydrite is omnipresent in environments and can influence the fate of Pb(II) during ferrihydrite transformation. Ferrihydrite is rarely pure and often coexists with impurities, which may influence the mineralogical changes of ferrihydrite and Pb(II) behavior. In this work, we investigated the effect of malic acid or phosphate on Pb(II)-ferrihydrite coprecipitates (Fh-Pb) transformation and the subsequent fate of Pb(II) during the 10-day aging of Fh-Pb. Results showed that both malic acid and phosphate retarded Fh-Pb transformation and prevented the release of Pb(II) from Fh-Pb back into solutions. Pb(II) was beneficial to goethite formation by inhibiting hematite formation while both malic acid and phosphate inhibited goethite formation since they could act as templates of nucleation. Besides, malic acid and phosphate improved the proportion of non-extracted Pb(II) during Fh-Pb transformation, indicating that Pb(II) was incorporated into secondary minerals. Pb(II) could not replace Fe(III) within the crystal lattice due to its large radius but was occluded into pores and defect structures within the secondary mineral lattices. This work can advance our understanding of the influences of malic acid and phosphate on Pb(II) immobility during Fh-Pb aging.

The discovery of plant biostimulants (PBs) in sewage sludge offers a promising avenue for biosolids valorization. Here, the study investigates how two mineral additives, including 2‐line ferrihydrite (a disordered iron oxide) and disordered birnessite (a manganese oxide), modulate microbial activity and molecular pathways to enhance PB production during aerobic sludge composting. Application of 2‐line ferrihydrite significantly promotes the synthesis of growth‐promoting PBs, including arginine, valine, decanoic acid, and indoleacetic acid (IAA), while disordered birnessite primarily enhances resistance‐related PBs, such as decanoic acid, L‐pyroglutamate, and trans‐aconitic acid. In pot trials, composted biosolids amended with 2‐line ferrihydrite significantly improve plant biomass and leaf area compared to mineral‐free and birnessite treatments. Metagenomic profiling reveals that PB biosynthesis is dominated by members of the phyla Pseudomonadota and Actinomycetota, with temporal niche partitioning across the thermophilic and maturation stages. 2‐line ferrihydrite enhances the abundance of critical biosynthetic genes (e.g., trpA/C/D/E/F), particularly within taxa such as Xanthomonadaceae, Sphingomonadaceae, and Streptosporangiaceae. Additionally, genes involved in IAA and indole biosysnthesis (ALDH, DDC, and tnaA) are enriched, supporting enhanced tryptophan‐to‐IAA conversion. This study provides a mechanistic link between iron oxide‐mediated microbial modulation and PB production in composted biosolids, offering a sustainable approach for upgrading waste into high‐value agricultural inputs. This study explores how iron and manganese oxides transform sewage sludge into plant biostimulants during composting. Non‐targeted identification reveals the main species of plant biostimulants. Metagenomic analysis reveals that 2‐line ferrihydrite specifically enriches microbial genes for biosynthesis, boosting plant‐growth promoters. Compost amended with this iron oxide enhances crop growth, providing a sustainable strategy for upgrading waste into high‐value agricultural inputs.

Iron oxides occur ubiquitously in environmental, geological, planetary, and technological settings. They exist in a rich variety of structures and hydration states. They are commonly fine-grained (nanophase) and poorly crystalline. This review summarizes recently measured thermodynamic data on their formation and surface energies. These data are essential for calculating the thermodynamic stability fields of the various iron oxide and oxyhydroxide phases and understanding their occurrence in natural and anthropogenic environments. The competition between surface enthalpy and the energetics of phase transformation leads to the general conclusion that polymorphs metastable as micrometer-sized or larger crystals can often be thermodynamically stabilized at the nanoscale. Such size-driven crossovers in stability help to explain patterns of occurrence of different iron oxides in nature.

Although, glyphosate (N-(phosphonomethyl) glycine) is one of the most widely used herbicides in the world, its interaction with poorly crystalline iron oxides, such as ferrihydrite, is not well studied. In this research, we examined the adsorption of glyphosate onto ferrihydrite using infrared spectroscopy (FT-IR), electron paramagnetic resonance spectroscopy (EPR), adsorption kinetic models and adsorption isotherm models. The effect of pH and sodium chloride concentration on the adsorption of glyphosate onto ferrihydrite as well as the effect of extractors (CaCl2 0.010 mol L−1 and Mehlich) on the desorption of glyphosate were also evaluated. There are two important findings described in this work. First, 84% of adsorbed glyphosate strongly interacted to ferrihydrite as an inner-sphere complex and phosphate and amine groups are involved in this interaction. Second, an increase of sodium chloride salt concentration increased the adsorption of glyphosate onto ferrihydrite. The non-linear Langmuir model and pseudo second order model showed a good agreement of theoretical limit of glyphosate adsorbed onto ferrihydrite, 54.88 µg mg−1 and 48.8 µg mg−1, respectively. The adsorption of glyphosate onto ferrihydrite decreased when the pH increased. Under the conditions used in this work, EPR spectra did not show dissolution of ferrihydrite. Surface area, pore volume and pHpzc of ferrihydrite decreased after adsorption of glyphosate.

Dimethyl arsonic acid, the most common organic arsenic pollutant, is widely present in the environment and seriously threatens the safety of drinking water. Syntheses of magnetite, magnetic bentonite, and magnetic ferrihydrite via hydrothermal methods, and the magnetic composites were examined using XRD, BET, VSM, and SEM. SEM images revealed that many monodispersible pellets were attached to the surface of magnetic bentonite. The magnetic ferrihydrite contained abundant pores and had a rich pore structure, which expanded the specific surface area of the original magnetite. The specific surface areas of the magnetic bentonite and magnetic ferrihydrite were 65.17 and 220.30 m 2 ·g −1 , respectively. The adsorption kinetics and adsorption isotherms of dimethyl arsonic acid on magnetic composites were studied. The adsorption of dimethyl arsonic acid on the magnetic composites conformed to the pseudo-second-order model and Freundlich isothermal adsorption model. By comparing the isotherms of the adsorption of dimethyl arsonic acid by the magnetic composites at pH values of 3, 7, and 11, respectively, it was found that the adsorption of dimethyl arsonic acid was the greatest at neutral pH of 7. The adsorption mechanism was analyzed via zeta potential determination, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The zeta potential results revealed that magnetic bentonite electrostatic activity occurred with dimethyl arsonic acid, and the magnetic ferrihydrite indicated a coordination complex with dimethyl arsonic acid. The XPS results revealed that the Fe–O bonds on the surfaces of the magnetic ferrihydrite had coordination complexation effects on the As-O of the dimethyl arsonic acid.

Nanophase Fe-oxyhydroxides in freshwater ferromanganese nodules (FFN) from Green Bay, Lake Michigan, and adsorbed arsenate have been investigated by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Z-contrast imaging, and ab initio calculations using the density functional theory (DFT). The samples from northern Green Bay can be divided into two types: Fe-Mn nodules and Fe-rich nodules. The manganese-bearing phases are todorokite, birnessite, and buserite. The iron-bearing phases are feroxyhyte, nanophase goethite, two-line ferrihydrite, and nanophase FeOOH with guyanaite structure. Z-contrast images of the Fe-oxyhydroxides show ordered FeOOH nano-domains with guyanaite structure intergrown with nanophase goethite. The FeOOH nanophase is a precursor to the goethite. Henceforth, we will refer to it as \"proto-goethite.\" DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest that ordering between Fe and vacancies in octahedral sites result in the transformation from feroxyhyte to goethite through a proto-goethite intermediate phase. Combining Z-contrast images and TEM-EDS reveals that arsenate (AsO43-) tetrahedra are preferentially adsorbed on the proto-goethite (001) surface via tridentate adsorption. Our study directly shows the atomic positions of Fe-oxyhydroxides with associated trace elements. The methods can be applied for identifying structures of nanophases and adsorbed trace elements and heavy metals.

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere.

Soil organic matter (SOM) often increases with the abundance of short-range-ordered iron (SRO Fe) mineral phases at local to global scales, implying a protective role for SRO Fe. However, less is known about how Fe phase composition and crystal order relate to SOM composition and turnover, which could be linked to redox alteration of Fe phases. We tested the hypothesis that the composition and turnover of mineral-associated SOM co-varied with Fe phase crystallinity and abundance across a well-characterized catena in the Luquillo Experimental Forest, Puerto Rico, using dense fractions from 30 A and B horizon soil samples. The δ¹³C and δ¹⁵N values of dense fractions were strongly and positively correlated (R² = 0.75), indicating microbial transformation of plant residues with lower δ¹³C and δ¹⁵N values. However, comparisons of dense fraction isotope ratios with roots and particulate matter suggested a greater contribution of plant versus microbial biomass to dense fraction SOM in valleys than ridges. Similarly, diffuse reflectance infrared Fourier transform spectroscopy indicated that SOM functional groups varied significantly along the catena. These trends in dense fraction SOM composition, as well as Δ¹⁴C values indicative of turnover rates, were significantly related to Fe phase crystallinity and abundance quantified with selective extractions. Mössbauer spectroscopy conducted on independent bulk soil samples indicated that nanoscale ordered Fe oxyhydroxide phases (nanogoethite, ferrihydrite, and/or very-SRO Fe with high substitutions) dominated (66–94%) total Fe at all positions and depths, with minor additional contributions from hematite, silicate and adsorbed FeII, and ilmenite. An additional phase that could represent organic-FeIII complexes or aluminosilicate-bearing FeIII was most abundant in valley soils (17–26% of total Fe). Overall, dense fraction samples with increasingly disordered Fe phases were significantly associated with increasingly plant-derived and faster-cycling SOM, while samples with relatively more-crystalline Fe phases tended towards slower-cycling SOM with a greater microbial component. Our data suggest that counter to prevailing thought, increased SRO Fe phase abundance in dynamic redox environments could facilitate transient accumulation of litter derivatives while not necessarily promoting long-term C stabilization.