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.

Traditional iron supplements for iron deficiency anemia (IDA) have several limitations, including suboptimal absorption, gastrointestinal discomfort, and concerns regarding long-term safety. In this study, we synthesized monodisperse 6-line ferrihydrite as an innovative iron supplement, featuring a structure analogous to the natural “iron core” present in ferritin. Notably, 6-line ferrihydrite (6-Fh) was internalized by Caco-2 cells via a process independent of divalent metal transporter 1 (DMT1). Additionally, its stability as nanoparticles within the gastrointestinal tract prevents the irritation typically associated with metal ions, thereby significantly enhancing iron utilization efficiency. Consequently, compared to FeSO₄ (a traditional oral iron supplement), 6-Fh effectively stabilized cellular free iron with low ROS toxicity and high biosafety, thereby effectively maintaining intestinal barrier integrity and avoiding liver injury. Furthermore, it restored intestinal dysbiosis caused by IDA and increased the proportion of beneficial bacterial strains, which was superior to FeSO₄. Characterized by low toxicity, efficient cellular absorption, intestinal stability, and superior iron supplementation efficacy compared with conventional iron supplements, 6-Fh demonstrates compelling therapeutic advantages and holds great promise for medical applications.Graphical Supplementary InformationThe online version contains supplementary material available at 10.1186/s12951-025-03814-z.

Perfluorooctane sulfonate (PFOS) is an emerging contaminant frequently detected in subsurface environments, raising significant concern due to its environmental persistence, mobility, and potential human health impacts. This study examines PFOS adsorption onto a range of solid substrates, including pure minerals, mineral assemblages, and natural soils. Specifically, the adsorption behavior of 2-line ferrihydrite, ferrihydrite-coated sand, and soil collected from a PFOS-impacted site in Killingworth, Connecticut was investigated to evaluate their capacity to retain PFOS under varying geochemical conditions. By integrating batch adsorption experiments with surface complexation modeling (SCM) and applying the component additivity approach, this study elucidates the reactive transport mechanisms governing PFOS behavior under a range of geochemical conditions. Our findings demonstrate that PFOS adsorption occurs significantly on both ferrihydrite and quartz surfaces, with the ferrihydrite-coated sand and soil exhibiting retention behavior attributable to contributions from both mineral phases. At lower pH values, sorption is predominantly governed by outer-sphere complexation driven by the surface charge characteristics of ferrihydrite. Specifically, under acidic conditions (pH < 5.5 for ferrihydrite-coated sand and pH < 6.0 for soil), PFOS retention is primarily facilitated through an outer-sphere hydrogen-bonded complex at ferrihydrite’s surface, while a secondary outer-sphere complex involving Na+ co-adsorption contributes to a lesser extent. At elevated pH levels, however, electrostatic interactions become less favorable, and non-electrostatic hydrophobic interactions with quartz surfaces become increasingly dominant, highlighting the transition in sorption mechanisms from charge-driven to hydrophobic partitioning under neutral to alkaline conditions. A comparison with traditional partitioning coefficients (Kd) revealed that their variability closely corresponds with changes in dominant surface complexes across different pH conditions. Given the critical role of solid-phase partitioning in governing PFAS transport in the subsurface, enhanced predictive capabilities are essential for advancing site-specific risk assessments and informing management strategies aimed at protecting both public and private water resources.Graphical abstractSupplementary InformationThe online version contains supplementary material available at 10.1186/s12932-025-00105-2.

Rice is consumed by ∼50% of the global population, grown primarily in flooded paddy fields, and is susceptible to arsenic accumulation. Inorganic arsenic, particularly in reduced form (As(III)), is considered the most toxic and is more likely to accumulate in rice grains under flooded systems. We postulate that increased levels of highly reactive iron minerals, such as ferrihydrite, in paddy soils can regulate the bioavailability of arsenic and reduce its uptake by priming iron plaque formation. To clarify, two rice varieties, Norin and Sabharaj, differing in arsenic uptake rate, were grown in paddy soil under flooded conditions with arsenate (As(V)) spiked-irrigation water. 2-line ferrihydrite was added at 0.00% (control), 0.05%, and 0.10% w/w and served as the highly reactive iron species. Irrespective of rice varieties, total inorganic arsenic (As(III) + As(V)) in grains in ferrihydrite systems decreased by 85 to 93% compared to the control. These results support ferrihydrite's intrinsic role in controlling paddy soils' rhizosphere chemistry. Our findings indicate that fresh reactive iron minerals are critical in the early formation of root iron plaque, which enhances the defense mechanism against arsenic. The findings may have implications for reducing toxic inorganic arsenic accumulation in lowland rice.

DNA adsorption onto mineral surfaces plays a crucial role in controlling its biogeochemical cycling, environmental stability, and accessibility for diverse environmental DNA (eDNA) applications. While eDNA exists in a wide range of polymer lengths, a limited understanding of how DNA polymer length influences adsorption and competition on mineral surfaces hinders accurate interpretations of its mobility and persistence in natural systems. Here, we address this knowledge gap by investigating the role of DNA polymer length (99 bp to ∼20,000 bp) on interactions with selected environmentally relevant minerals, including Fe(III)-(oxyhydr)oxides (goethite, 2-line ferrihydrite), clays (kaolinite, montmorillonite) and hydroxyapatite. Controlled batch experiments at neutral pH show that adsorption from model uniform DNA solutions increases with increasing polymer length for Fe(III)-(oxyhydr)oxides and clays, with the reverse trend observed for hydroxyapatite. During competitive adsorption experiments (using 99 and 2000 bp DNA), the order of addition influenced the extent of adsorption. However, under simultaneous addition─closely reflecting natural environmental conditions, where both polymers compete for binding sites─shorter DNA polymers exhibited preferential adsorption across all minerals. We hypothesize that this preferential adsorption may contribute toward the enhanced environmental persistence of shorter DNA polymers, including the exclusive preservation of small DNA polymers (<100 bp) over long time scales. These findings underscore the critical role of polymer length in DNA adsorption and provide a basis for mechanistic insights into the factors influencing its preservation and fate in natural environments with implications for a range of DNA-based technologies.

Fast phase transformation of 2-line ferrihydrite to hematite as induced by the injection of photoelectrons

Phosphorus (P), a non-renewable resource essential for sustaining life, faces increasing environmental losses from agricultural systems. However, the effects of flavonoid-induced iron oxide on soil P behavior remain poorly understood, particularly in paddy soils. Here, we conducted a 7-year field trial under four fertilization regimes combined with laboratory incubations to reveal how flavonoid-modified iron oxides regulate P at the molecular scale. Results showed that manure-applied (NPKM) soils increased the content of flavonoids by 48.7% and short-range-order minerals (SROs) by 8.7% compared with chemically fertilized (NPK) soils. Through interfacial reactions between Fe-P minerals and quercetin, the formation of 2-line ferrihydrite was promoted by quercetin with an interplanar distance of 0.26/0.30 nm at pH 7. It was found that 14.25% of the Fe-phosphate group was incorporated at a quercetin concentration of 1 mM, and Fe oxides acted as the "core" for retaining P in these complexes. Further, phosphate release was observed during the interfacial reaction with increasing quercetin concentrations, suggesting a potential trade-off between P fixation and release. Despite these benefits, NPKM soils exhibited the highest degree of phosphorus saturation (DPS) (18.61%) and the lowest soil phosphorus storage capacity (1.70 mg kg-1), indicating an elevated risk of P loss. A significant positive correlation was identified among SROs, flavonoids, and DPS in paddy soils. Collectively, our findings demonstrate that flavonoids can modify the morphology of Fe oxides in paddy soils, thereby enhancing P fixation. This presents a promising approach for mitigating diffuse P pollution and promoting sustainable agriculture.

Seasonal variations of drainage waters and ochreous products of their discharge from the closed abandoned old gallery at the Grantcharitsa scheelite deposit (Bulgaria) were studied by field and laboratory methods for the period 2019–2023. The drainage is generated under anoxic conditions and is inherently diluted (EC = 100–202 µS/cm) with S (6–12 mg/L), Si (6–22 mg/L), Na (6–10 mg/L), Fe (0.2–3.3 mg/L), and W (0.19–3.5 µg/L), at a pH 4.4–6.5 and temperature 7–11.5 °C, with dissolved oxygen DO (2.1–7.7 mg/L). The concentrations of Fe and W and the pH of the water are variable and reach their maximum values during the dry (autumn) season. It was found that such parameters as pH, Eh, DO, Fe and W content change dramatically at a distance of up to 3 m from the water outlet; the values of pH, DO and Eh are sharply increased with a simultaneous nearly 5–6-times reduction in iron and tungsten content. The decrease in the contents of these elements is associated with the precipitation of ochreous material consisting of nanoscale ferrihydrite with an intermediate structural ordering between 2-line and 6-line ferrihydrite (major phase), hematite, goethite, quartz, montmorillonite and magnetite. The formation of ferrihydrite occurs as a result of abiotic and biotic processes with the participation of iron-oxidizing bacteria. Besides Fe2O3 (55.5–64.0 wt.%), the ochreous sediment contains SiO2 (12.0–16.4 wt.%), SO3 (1.3–2.4 wt.%), Al2O3 (3.1–6.8 wt.%) and WO3 (0.07–0.11 wt.%). It has been shown that drainage waters and ochreous sediments do not inherently have a negative impact on the environment. The environmental problem arises with intense snowmelt and heavy rainfall, as a result of which the accumulated sediments are washed away and carried in the form of suspensions into the water systems. It is suggested that by providing atmospheric oxygen access to the closed gallery (via local boreholes), it is possible to stop the generation of iron-enriched drainage.

The formation of energetically favorable and metastable mineral phases within the Fe-H2O system controls the long-term mobility of iron complexes in natural aquifers and other environmentally and industrially relevant systems. The fundamental mechanism controlling the formation of these phases has remained enigmatic. We develop a general partial equilibrium model, leveraging recent synchrotron-based data on the time evolution of solid Fe(III) hydroxides along with aqueous complexes. We combine thermodynamic considerations and particle-morphology-dependent kinetic rate equations under full consideration of the aqueous phase in disequilibrium with one or more of the forming minerals. The new model predicts the rate of amorphous 2-line ferrihydrite precipitation, dissolution, and overall transformation to crystalline goethite. It is found that the precipitation of goethite (i) occurs from solution and (ii) is limited by the comparatively slow dissolution of the first forming amorphous phase 2-line ferrihydrite. A generalized transformation mechanism further illustrates that differences in the kinetics of Fe(III) precipitation are controlled by the coordination environment of the predominant Fe(III) hydrolysis product. The framework allows modeling of other iron(bearing) phases across a broad range of aqueous phase compositions.

The long-term transformation of FeIII-AsV coprecipitates at room temperature under oxic conditions: New insights for the fate and the speciation of As

Effects of gamma(γ)-irradiation on the physicochemical properties and bioavailability of iron oxyhydroxides coprecipitated with varying concentrations of Na-alginate

Arsenic pollution is a public health hazard in Burkina Faso due to its impact on human health and water resources. To mitigate this pollution, ferrihydrite material has been synthesized and characterized to be used as adsorbent for arsenic removal in aqueous solutions. This study aimed to contribute to improve of access to clean drinking water by removing arsenic from water using ferrihydrite. Arsenic species such as As(III) and As(V) were removed through batch adsorption. Experiments were carried out in batch mode using arsenic aqueous solutions. The characterization of ferrihydrite using Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDX), X-ray Diffraction (XRD), Infrared (IR), and Brunauer Emmett Teller (BET) showed that an amorphous and microporous 2-line ferrihydrite. The total specific surface area and pH at point of zero charge (pHpzc) were 184.518 m²/g and 9.41, respectively. The optimal adsorbent doses were 4 g/L for As (V) and 8 g/L for As (III). The optimum pH range for the adsorption of As (V) and As (III) was between 2 and 10, The maximum adsorption capacity was 15.07 mg/g for As(V) and 13.01 mg/g for As(III) with increasing concentration between 2 and 16 mg/L. Equilibrium time for As (V) and As (III) on ferrihydrite was found to be 720 min and 960 min, respectively. The adsorption of As(V) and As(III) was consistent with the Langmuir monolayer model on ferrihydrite. Arsenic adsorption was occurred according to spontaneous chemical reaction. Arsenic removal was occurred on a monolayer following the pseudo-second order kinetic.

In a boreal acidic sulfate-rich subsoil (pH 3-4) developing on sulfidic and organic-rich sediments over the past 70 years, extensive brownish-to-yellowish layers have formed on macropores. Our data reveal that these layers ("macropore surfaces") are strongly enriched in 1 M HCl-extractable reactive iron (2-7% dry weight), largely bound to schwertmannite and 2-line ferrihydrite. These reactive iron phases trap large pools of labile organic matter (OM) and HCl-extractable phosphorus, possibly derived from the cultivated layer. Within soil aggregates, the OM is of a different nature from that on the macropore surfaces but similar to that in the underlying sulfidic sediments (C-horizon). This provides evidence that the sedimentary OM in the bulk subsoil has been largely preserved without significant decomposition and/or fractionation, likely due to physiochemical stabilization by the reactive iron phases that also existed abundantly within the aggregates. These findings not only highlight the important yet underappreciated roles of iron oxyhydroxysulfates in OM/nutrient storage and distribution in acidic sulfate-rich and other similar environments but also suggest that boreal acidic sulfate-rich subsoils and other similar soil systems (existing widely on coastal plains worldwide and being increasingly formed in thawing permafrost) may act as global sinks for OM and nutrients in the short run.

Radiation-chemical synthesis and characterization of ferrihydrite from iron (III) nitrate

Harmful levels of environmental contaminants, such as arsenic (As), persist readily in the environment, threatening safe drinking water supplies in many parts of the world. In this paper, we present a straightforward and cost-effective filtration technology for the removal of arsenate from potable water. Biocomposite filters comprised of nanocrystalline iron oxides or oxyhydroxides mineralized within lignocellulose scaffolds constitute a promising low cost, low-tech avenue for the removal of these contaminants. Two types of iron oxide mineral phases, 2-line ferrihydrite (Fh) and magnetite (Mt), were synthesized within highly porous balsa wood using an environmentally benign modification process and studied in view of their effective removal of As from contaminated water. The mineral deposition pattern, minerology, as well as crystallinity, were assessed using scanning electron microscopy, transmission electron microscopy, micro-computed X-ray tomography, confocal Raman microscopy, infrared spectroscopy, and X-ray powder diffraction. Our results indicate a preferential distribution of the Fh mineral phase within the micro-porous cell wall and radial parenchyma cells of rays, while Mt is formed primarily at the cell wall/lumen interface of vessels and fibers. Water samples of known As concentrations were subjected to composite filters in batch incubation and gravity-driven flow-through adsorption tests. Eluents were analyzed using microwave plasma optical emission spectroscopy (MP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). By subjecting the filters to a flow of contaminated water, the time for As uptake was reduced to minutes rather than hours, while immobilizing the same amount of As. The retention of As within the composite filter was further confirmed through energy-dispersive X-ray mappings. Apart from addressing dangerously high levels of arsenate in potable water, these versatile iron oxide lignocellulosic filters harbor tremendous potential for addressing current and emerging environmental contaminants that are known to adsorb on iron oxide mineral phases, such as phosphate, polycyclic aromatic hydrocarbons or heavy metals.

The transformation of 2-line ferrihydrite to goethite from supersaturated solutions at alkaline pH ≥ 13.0 was studied using a combination of benchtop and advanced synchrotron techniques such as X-ray diffraction, thermogravimetric analysis, and X-ray absorption spectroscopy. In comparison to the transformation rates at acidic to mildly alkaline environments, the half-life, t1/2, of 2-line ferrihydrite reduces from several months at pH = 2.0, and approximately 15 days at pH = 10.0, to just under 5 h at pH = 14.0. The calculated-first order rate constants of transformation, k, increase exponentially with respect to the pH and follow the progression log10 k = log10 k0 + a·pH3. Simultaneous monitoring of the aqueous Fe(III) concentration via inductively coupled plasma optical emission spectroscopy demonstrates that (i) goethite likely precipitates from solution and (ii) its formation is rate-limited by the comparatively slow redissolution of 2-line ferrihydrite. The analysis presented can be used to estimate the transformation rate of naturally occurring 2-line ferrihydrite in aqueous electrolytes characteristic to mine and radioactive waste tailings as well as the formation of corrosion products in cementitious pore solutions.

Molecular-scale insight into selenium isotope fractionation caused by adsorption on Fe (oxyhydr)oxides

The terrestrial serpentinite-hosted ecosystem known as “The Cedars” is home to a diverse microbial community persisting under highly alkaline (pH ~ 12) and reducing (Eh < −550 mV) conditions. This extreme environment presents particular difficulties for microbial life, and efforts to isolate microorganisms from The Cedars over the past decade have remained challenging. Herein, we report the initial physiological assessment and/or full genomic characterization of three isolates: Paenibacillus sp. Cedars (‘Paeni-Cedars’), Alishewanella sp. BS5-314 (‘Ali-BS5-314’), and Anaerobacillus sp. CMMVII (‘Anaero-CMMVII’). Paeni-Cedars is a Gram-positive, rod-shaped, mesophilic facultative anaerobe that grows between pH 7–10 (minimum pH tested was 7), temperatures 20–40°C, and 0–3% NaCl concentration. The addition of 10–20 mM CaCl2 enhanced growth, and iron reduction was observed in the following order, 2-line ferrihydrite > magnetite > serpentinite ~ chromite ~ hematite. Genome analysis identified genes for flavin-mediated iron reduction and synthesis of a bacillibactin-like, catechol-type siderophore. Ali-BS5-314 is a Gram-negative, rod-shaped, mesophilic, facultative anaerobic alkaliphile that grows between pH 10–12 and temperatures 10–40°C, with limited growth observed 1–5% NaCl. Nitrate is used as a terminal electron acceptor under anaerobic conditions, which was corroborated by genome analysis. The Ali-BS5-314 genome also includes genes for benzoate-like compound metabolism. Anaero-CMMVII remained difficult to cultivate for physiological studies; however, growth was observed between pH 9–12, with the addition of 0.01–1% yeast extract. Anaero-CMMVII is a probable oxygen-tolerant anaerobic alkaliphile with hydrogenotrophic respiration coupled with nitrate reduction, as determined by genome analysis. Based on single-copy genes, ANI, AAI and dDDH analyses, Paeni-Cedars and Ali-BS5-314 are related to other species (P. glucanolyticus and A. aestuarii, respectively), and Anaero-CMMVII represents a new species. The characterization of these three isolates demonstrate the range of ecophysiological adaptations and metabolisms present in serpentinite-hosted ecosystems, including mineral reduction, alkaliphily, and siderophore production.

Chelated heavy metals removal by in-situ formed Fe(II) and Fe(III) iron (oxy)hydroxides: Mechanism and performance

BackgroundAsbestos is a fibrous mineral that was widely used in the past. However, asbestos inhalation is associated with an aggressive type of cancer known as malignant mesothelioma (MM). After inhalation, an iron-rich coat forms around the asbestos fibres, together the coat and fibre are termed an “asbestos ferruginous body” (AFB). AFBs are the main features associated with asbestos-induced MM. Whilst several studies have investigated the external morphology of AFBs, none have characterised the internal morphology. Here, cross-sections of multiple AFBs from two smokers and two non-smokers are compared to investigate the effects of smoking on the onset and growth of AFBs. Morphological and chemical observations of AFBs were undertaken by transmission electron microscopy, energy dispersive x-ray spectroscopy and selected area diffraction.ResultsThe AFBs of all patients were composed of concentric layers of 2-line or 6-line ferrihydrite, with small spherical features being observed on the outside of the AFBs and within the cross-sections. The spherical components are of a similar size to Fe-rich inclusions found within macrophages from mice injected with asbestos fibres in a previous study. As such, the spherical components composing the AFBs may result from the deposition of Fe-rich inclusions during frustrated phagocytosis. The AFBs were also variable in terms of their Fe, P and Ca abundances, with some layers recording higher Fe concentrations (dense layers), whilst others lower Fe concentrations (porous layers). Furthermore, smokers were found to have smaller and overall denser AFBs than non-smokers.ConclusionsThe AFBs of smokers and non-smokers show differences in their morphology, indicating they grew in lung environments that experienced disparate conditions. Both the asbestos fibres of smokers and non-smokers were likely subjected to frustrated phagocytosis and accreted mucopolysaccharides, resulting in Fe accumulation and AFB formation. However, smokers’ AFBs experienced a more uniform Fe-supply within the lung environment compared to non-smokers, likely due to Fe complexation from cigarette smoke, yielding denser, smaller and more Fe-rich AFBs. Moreover, the lack of any non-ferrihydrite Fe phases in the AFBs may indicate that the ferritin shell was intact, and that ROS may not be the main driver for the onset of MM.