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This study deals with the identification of the factors that affect pyrite oxidation in acid mine drainage conditions. For this scope, weathering experiments have been carried at laboratory scale based on the design of experiments methodology to evaluate the effect of factors such as major ion concentrations, crystal size, and humic acids presence over the amount of elemental sulfur produced due to the involved weathering reactions. In particular, metal and anionic concentrations in solution were quantified by inductively coupled plasma-atomic emission spectroscopy and ion-chromatography techniques, respectively, whereas the amount of elemental sulfur was quantified with a high-performance liquid chromatography with diode-array detection technique after proper extraction procedure. A partial least squares regression was calculated to establish a quantitative relationship between the considered factors and the amount of elemental sulfur. After evaluation of the model, ferric iron, crystal size and the presence of humic acids were identified as the relevant factors for pyrite oxidation under acidic conditions. In addition, the surface of the samples was characterized by Raman imaging spectroscopy and subsequently analyzed by explorative hyperspectral analysis methods to assess the spatial distribution of the elemental sulfur as the main weathering product, resulting in a homogenous distribution.

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Previous studies have reported the role of some species of acidophilic bacteria in accelerating the dissolution of goethite under aerobic and anaerobic conditions. This has relevance for environments impacted by acid mine drainage and for the potential bioleaching of limonitic laterite ores. In this study, natural well-characterized goethite mineral samples and synthetic goethite were used in aerobic and anaerobic laboratory batch culture incubation experiments with ferric iron-reducing, acidophilic bacteria, including the lithoautotrophic species Acidithiobacillus (At.) thiooxidans, At. ferrooxidans, and At. caldus, as well as two strains of the organoheterotrophic species Acidiphilium cryptum. All bacteria remained alive throughout the experiments and efficiently reduced soluble ferric iron in solution in positive control assays. However, goethite dissolution was low to negligible in all experimental assays with natural goethite, while some dissolution occurred with synthetic goethite in agreement with previous publications. The results indicate that ferric iron-reducing microbial activity at low pH is less relevant for goethite dissolution than the oxidation of elemental sulfur to sulfuric acid. Microbial ferric iron reduction enhances but does not initiate goethite dissolution in very acidic liquors.

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The supply and control of iron is essential for all cells and vital for many physiological processes. All functions and activities of iron are expressed in conjunction with iron-binding molecules. For example, natural chelators such as transferrin and chelator-iron complexes such as haem play major roles in iron metabolism and human physiology. Similarly, the mainstay treatments of the most common diseases of iron metabolism, namely iron deficiency anaemia and iron overload, involve many iron-chelator complexes and the iron-chelating drugs deferiprone (L1), deferoxamine (DF) and deferasirox. Endogenous chelators such as citric acid and glutathione and exogenous chelators such as ascorbic acid also play important roles in iron metabolism and iron homeostasis. Recent advances in the treatment of iron deficiency anaemia with effective iron complexes such as the ferric iron tri-maltol complex (feraccru or accrufer) and the effective treatment of transfusional iron overload using L1 and L1/DF combinations have decreased associated mortality and morbidity and also improved the quality of life of millions of patients. Many other chelating drugs such as ciclopirox, dexrazoxane and EDTA are used daily by millions of patients in other diseases. Similarly, many other drugs or their metabolites with iron-chelation capacity such as hydroxyurea, tetracyclines, anthracyclines and aspirin, as well as dietary molecules such as gallic acid, caffeic acid, quercetin, ellagic acid, maltol and many other phytochelators, are known to interact with iron and affect iron metabolism and related diseases. Different interactions are also observed in the presence of essential, xenobiotic, diagnostic and theranostic metal ions competing with iron. Clinical trials using L1 in Parkinson's, Alzheimer's and other neurodegenerative diseases, as well as HIV and other infections, cancer, diabetic nephropathy and anaemia of inflammation, highlight the importance of chelation therapy in many other clinical conditions. The proposed use of iron chelators for modulating ferroptosis signifies a new era in the design of new therapeutic chelation strategies in many other diseases. The introduction of artificial intelligence guidance for optimal chelation therapeutic outcomes in personalised medicine is expected to increase further the impact of chelation in medicine, as well as the survival and quality of life of millions of patients with iron metabolic disorders and also other diseases.

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The involvement of the immune oxidative stress response in the pathophysiology and pathogenesis of allergic asthma is well documented. However, reports on the role of iron homeostasis in allergic asthma is scarce. Therefore, this study aims to identify iron-related genes and proteins in mouse models of allergic asthma. Related articles were identified from SCOPUS and Web of Science databases. The article search was limited to publications in English, within a 10-year period (2014 - 2023, up to 16 August 2023) and original/research papers. All identified articles were screened for eligibility using the inclusion and exclusion criteria. All eligible articles were quality appraised prior to data extraction. Five studies were selected for data extraction. Based on the extracted data, three themes and seven subthemes related to iron homeostasis were identified. The type of samples and analytical methods used were also identified. In conclusion, our study elucidates that iron-related proteins are regulated in animal models of allergic asthma. However, the currently available data do not allow us to conclude whether the disease model resulted in iron accumulation or depletion. Therefore, further studies with other related markers should be conducted.

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In the framework of the H2020 project CROCODILE, the recovery of Co from oxidized ores by reductive bioleaching has been studied. The objective was to reduce Fe(III) to Fe(II) to enhance the dissolution of Co from New-Caledonian limonitic laterites, mainly composed of goethite and Mn oxides. This study focused on the Fe(III) bioreduction which is a relevant reaction of this process. In the first step, biomass growth was sustained by aerobic bio-oxidation of elemental sulfur. In the second step, the biomass anaerobically reduced Fe(III) to Fe(II). The last step, which is not in the scope of this study, was the reduction of limonites and the dissolution of metals. This study aimed at assessing the Fe(III) bioreduction rate at 35°C with a microbial consortium composed predominantly of Sulfobacillus (Sb.) species as the iron reducers and Acidithiobacillus (At.) caldus. It evaluated the influence of the biomass concentration on the Fe(III) bioreduction rate and yield, both in batch and continuous mode. The influence of the composition of the growth medium on the bioreduction rate was assessed in continuous mode. A mean Fe(III) bioreduction rate of 1.7 mg·L-1·h-1 was measured in batch mode, i.e., 13 times faster than the abiotic control (0.13 mg·L-1·h-1). An increase in biomass concentrations in the liquid phase from 4 × 108 cells·mL-1 to 3 × 109 cells·mL-1 resulted in an increase of the mean Fe(III) bioreduction rate from 1.7 to 10 mg·L-1·h-1. A test in continuous stirred tank reactors at 35°C resulted in further optimization of the Fe(III) bioreduction rate which reached 20 mg·L-1·h-1. A large excess of nutrients enables to obtain higher kinetics. The determination of this kinetics is essential for the design of a reductive bioleaching process.

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Iron-rich phosphorus (P) sorption materials (PSMs) are often used in P removal structures, a best management practice able to sequester dissolved P from surface runoff, subsurface drainage, and wastewater. The use of bottom-upward flow in these structures is of great interest, but it creates an intrinsic complication: the presence of stagnant water between flow events may cause structures to develop anoxic conditions. It is unknown whether the redox sensitivity of iron (Fe), the predominant element in Fe-rich PSMs, will affect P binding under anoxic conditions. Understanding the potential impact of intermittent anoxic conditions on the solubility of previously adsorbed P is imperative for determining the feasibility of the bottom-up flow design. The objective of this research was to investigate the (1) development of anoxic conditions in the presence of Fe-rich PSM and tile drainage, (2) Fe-bound P mobilization and solubility, and (3) changes in P sorption capacity of Fe-rich PSMs after oxic conditions are restored. Three Fe-rich PSMs were tested in batch incubation studies: acid mine drainage residual, Fe-coated alumina, and steel metal shavings. Non-treated and P-treated PSM samples were incubated in biogeochemical reactors for as long as necessary to reach Eh = -200 mV. After incubation, dissolved P concentrations in P-treated samples and non-treated samples were similarly low, indicating stability of P retention of PSMs under anoxic conditions. The P removal ability of non-treated PSMs before and after undergoing incubation was not significantly altered, as determined in flow-through experiments. Potentially harmful trace metals were not detected in the incubated solutions. Our research shows that the development of anoxic conditions does not significantly impact PSMs Fe-bound P dissolution, and the P removal ability of PSMs persists after oxic conditions are reestablished.

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Microbial acquisition and utilization of organic and mineral phosphorus (P) sources in paddy soils are strongly dependent on redox environment and remain the key to understand P turnover and allocation for cell compound synthesis. Using double 32/33P labeling, we traced the P from three sources in a P-limited paddy soil: ferric iron-bound phosphate (Fe-P), wheat straw P (Straw-P), and soil P (Soil-P) in microbial biomass P (MBP) and phospholipids (Phospholipid-P) of individual microbial groups depending on water regimes: (i) continuous flooding or (ii) alternate wetting and drying. 32/33P labeling combined with phospholipid fatty acid analysis allowed to trace P utilization by functional microbial groups. Microbial P nutrition was mainly covered by Soil-P, whereas microorganisms preferred to take up P from mineralized Straw-P than from Fe-P dissolution. The main Straw-P mobilizing agents were Actinobacteria under alternating wetting and drying and other Gram-positive bacteria under continuous flooding. Actinobacteria and arbuscular mycorrhiza increased P incorporation into cell membranes by 1.4-5.8 times under alternate wetting and drying compared to continuous flooding. The Fe-P contribution to MBP was 4-5 times larger in bulk than in rooted soil because (i) rice roots outcompeted microorganisms for P uptake from Fe-P and (ii) rhizodeposits stimulated microbial activity, e.g. phosphomonoesterase production and Straw-P mineralization. Higher phosphomonoesterase activities during slow soil drying compensated for the decreased reductive dissolution of Fe-P. Concluding, microbial P acquisition strategies depend on (i) Soil-P, especially organic P, availability, (ii) the activity of phosphomonoesterases produced by microorganisms and roots, and (iii) P sources - all of which depend on the redox conditions. Maximizing legacy P utilization in the soil as a function of the water regime is one potential way to reduce competition between roots and microbes for P in rice cultivation.

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Colloidal phosphorus (P) is an important P form in agricultural runoff and can threaten water quality. However, up to date, there are few effective approaches to mitigate colloidal P pollution. This study investigated the effect of ultraviolet (UV) irradiation on medium-colloidal (MC; 220 nm-450 nm) and fine-colloidal (FC; 3 kDa-220 nm) P in agricultural runoff. Under 24 h of UV irradiation, as the most abundant colloidal P fraction, concentration of total P (TP) in FC consistently decreased by 81.0%, while TP concentration in MC first increased by 74.4% after 3 h and then decreased with irradiation time. At the same time, particulate TP (>450 nm) concentration was found to be increased from 0 to 14.7 µM. However, there were no obvious variations in TP concentrations in FC and MC fractions under dark conditions. In FC fraction, with the decrease of TP, the corresponding concentrations of iron (Fe), aluminum (Al), silicon (Si) declined synchronously, and ferric iron/ferrous iron (Fe(III)/Fe(II)) ratio and organic matter (OM) concentration were reduced as well. These results suggested that P in FC fraction was gradually transformed into particulate P during photoreduction of Fe(III) and photodegradation of OM under UV irradiation. Our study helps to understand the mechanism of the phototransformation of colloidal P, and propose an UV irradiation-based approach to remove colloidal P in agricultural runoff.

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Three novel strains in the genus Shewanella, designated A3AT, C31T and C32, were isolated from mangrove sediment samples. They were facultative anaerobic, Gram-stain-negative, rod-shaped, flagellum-harbouring, oxidase- and catalase-positive, electrogenic and capable of using Fe(III) as an electron acceptor during anaerobic growth. Results of phylogenetic analysis based on 16S rRNA gene and genomic sequences revealed that the strains should be assigned to the genus Shewanella. The 16S rRNA gene similarity, average nucleotide identity (ANI) and digital DNA-DNA hybridization (dDDH) values between the isolates and their closely related species were below the respective cut-off values for species differentiation. The 16S rRNA gene similarity, ANI and dDDH values between strains C31T and C32 were 99.7, 99.9 and 99.9 %, respectively, indicating that they should belong to the same genospecies. Based on polyphasic taxonomic approach, two novel species are proposed, Shewanella ferrihydritica sp. nov. with type strain A3AT (GDMCC 1.2732T=JCM 34899T) and Shewanella electrica sp. nov. with type strain C31T (GDMCC 1.2736T=JCM 34902T).

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Siderophores are important for ferric iron solubilization, sequestration, transportation, and storage, especially under iron-limiting conditions such as aerobic conditions at high pH. Siderophores are mainly produced by non-ribosomal peptide synthetase-dependent siderophore pathway, non-ribosomal peptide synthetase-independent siderophore synthetase pathway, or the hybrid non-ribosomal peptide synthetases/non-ribosomal peptide synthetases-independent siderophore pathway. Outcompeting or inhibition of plant pathogens, alteration of host defense mechanisms, and alteration of plant-fungal interactions have been associated with fungal siderophores. To understand these mechanisms in fungi, studies have been conducted on siderophore biosynthesis by ascomycetes with limited focus on the basidiomycetes. Armillaria includes several species that are pathogens of woody plants and trees important to agriculture, horticulture, and forestry. The aim of this study was to investigate the presence of non-ribosomal peptide synthetases-independent siderophore synthetase gene cluster(s) in genomes of Armillaria species using a comparative genomics approach. Iron-dependent growth and siderophore biosynthesis in strains of selected Armillaria spp. were also evaluated in vitro. Two distinct non-ribosomal peptide synthetases-independent siderophore synthetase gene clusters were identified in all the genomes. All non-ribosomal peptide synthetases-independent siderophore synthetase genes identified putatively encode Type A' non-ribosomal peptide synthetases-independent siderophore synthetases, most of which have IucA_IucC and FhuF-like transporter domains at their N- and C-terminals, respectively. The effect of iron on culture growth varied among the strains studied. Bioassays using the CAS assay on selected Armillaria spp. revealed in vitro siderophore biosynthesis by all strains irrespective of added FeCl3 concentration. This study highlights some of the tools that Armillaria species allocate to iron homeostasis. The information generated from this study may in future aid in developing molecular based methods to control these phytopathogens.

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Iron acquisition is an essential process of cell physiology for biological systems. In Klebsiella pneumoniae, the siderophore and ferric-acquisition ABC (ATP-Binding-Cassette) transporter KfuABC is utilized for iron uptake. Initial recognition of the various ferric sources in periplasm and transportation across the cytoplasmic membrane is performed by the substrate-binding protein (SBP) KfuA. Here we report the 2.0 Å resolution crystal structure of KfuA from K. pneumoniae, which crystallizes in the space group P1211 with a single monomer in the asymmetric unit. A bound metal ion reveals the residues required for binding ferric ions. Binding analysis shows that ferric iron and the iron-mimicking gallium bind with high affinity to KfuA. Growth curves show that gallium inhibits growth of K. pneumoniae whereas ferric iron enhances it. This work suggests a mechanism whereby gallium effectively competes with ferric iron, disrupting iron-dependent biological functions via binding to KfuA and leading to heightened antimicrobial efficacy. Significantly, humans lack equivalent ABC transporters like SBP KfuA, underscoring the potential of KfuA as an attractive target for therapeutic intervention.

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Glyphosate, the most used herbicide in the world, has a residue problem that cannot be ignored. However, glyphosate itself does not have fluorescence emission and lacks the conditions for fluorescence detection. In this work, a rapid and selective fluorescence detection method of glyphosate was designed by an 'on-off-on' fluorescent switch based on a luminous covalent organic framework (L-COF). Only the fixed concentration of Fe3+ as an intermediate could trigger the fluorescent switch and no incubation step was required. The proposed method showed good accuracy with a correlation coefficient of 0.9978. The method's limits of detection and quantitation were 0.88 and 2.93 µmol/L, which were lower than the maximum allowable residue limits in some regulations. Environmental water samples and tomatoes were selected as actual samples to verify the application in a complex matrix. A satisfactory mean recovery from 87% to 106% was gained. Furthermore, Fe3+ could induce fluorescence quenching of L-COF through the photo-induced electron transfer (PET) effect, while the addition of glyphosate could block the PET effect to achieve detection. These results demonstrated the proposed method had abilities to detect glyphosate and broaden the application of L-COF.

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Fomitiporia mediterranea (Fmed) is the primary Basidiomycota species causing white rot in European vineyards affected by the Esca complex of diseases (ECD). In the last few years, an increasing number of studies have highlighted the importance of reconsidering the role of Fmed in ECD etiology, justifying an increase in research interest related to Fmed's biomolecular pathogenetic mechanisms. In the context of the current re-evaluation of the binary distinction (brown vs. white rot) between biomolecular decay pathways induced by Basidiomycota species, our research aims to investigate the potential for non-enzymatic mechanisms adopted by Fmed, which is typically described as a white rot fungus. Our results demonstrate how, in liquid culture reproducing nutrient restriction conditions often found in wood, Fmed can produce low molecular weight compounds, the hallmark of the non-enzymatic "chelator-mediated Fenton" (CMF) reaction, originally described for brown rot fungi. CMF reactions can redox cycle with ferric iron, generating hydrogen peroxide and ferrous iron, necessary reactants leading to hydroxyl radical (•OH) production. These observations led to the conclusion that a non-enzymatic radical-generating CMF-like mechanism may be utilized by Fmed, potentially together with an enzymatic pool, to contribute to degrading wood constituents; moreover, indicating significant variability between strains.

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Microbes affect arsenic accumulation in the arsenic-hyperaccumulator Pteris vittata, but the associated molecular mechanism remains uncertain. Here, we investigated the effect of Enterobacter sp. E1 on arsenic accumulation by P. vittata. Strain E1 presented capacities of arsenate [As(V)] and Fe(III) reduction during cultivation. In the pot experiment with P. vittata, the biomass, arsenic content, and chlorophyll content of P. vittata significantly increased by 30.03%, 74.9%, and 112.1%, respectively. Strikingly, the water-soluble plus exchangeable arsenic (WE-As) significantly increased by 52.05%, while Fe-bound arsenic (Fe-As) decreased by 29.64% in the potted soil treated with strain E1. The possible role of activation of arsenic by strain E1 was subsequently investigated by exposing As(V)-absorbed ferrihydrite to the bacterial culture. Speciation analyses of As showed that strain E1 significantly increased soluble levels of As and Fe and that more As(V) was reduced to arsenite. Additionally, increased microbial diversity and soil enzymatic activities in soils indicated that strain E1 posed few ecological risks. These results indicate that strain E1 effectively increased As accumulation in P. vittata mainly by promoting plant growth and dissolving soil arsenic. Our findings suggest that As(V) and Fe(III)-reducer E1 could be used to enhance the phytoremediation of P. vittata in arsenic-contaminated soils.

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Steel is used as reinforcement in construction materials and it is also an important component of cement-stabilized waste materials to be disposed of in deep geological repositories for radioactive waste. Steel corrosion releases dissolved Fe(II/III) species that can form corrosion products on the steel surface or interact with cementitious materials at the iron-cement interface. The thermodynamically stable Fe species in the given conditions may diffuse further into the adjacent, porous cement matrix and react with individual cement phases. Thus, the retention of Fe(II/III) by the hydrate assemblage of cement paste is an important process affecting the diffusive transport of the aqueous species into the cementitious materials. The diffusion of aqueous Fe(II/III) species from the steel surface into the adjacent cementitious material coupled with the kinetically controlled formation of iron corrosion products, such as by Fe(II) oxidation, decisively determines the extension of the corrosion front. This review summarises the state-of-the art knowledge on the interaction of ferrous and ferric iron with cement phases based on a literature survey and provides new insights and proper perspectives for future study on interaction systems of iron and cement.

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The effect of ferric iron (Fe(Ш)) on the performance of heterotrophic solid-phase denitrification (SPD) using biodegradable polymer composite as the electron donor was investigated. The results of continuous batch experiments showed that the addition of over 10 mg/L Fe(Ш) significantly inhibited nitrate removal and led to the accumulation of nitrite. The addition of Fe(Ш) reduced the microbial community diversity and shifted the community dominated by complete denitrifiers (e.g. Thauera) to that dominated by incomplete denitrifiers (e.g. Thermomonas, Stenotrophomonas and Sphingomonas). The predicted analysis of microbial function by PICRUSt2 indicated that the relative abundance of denitrifying genes, including napA/B, nirS and nosZ, were remarkably reduced in the Fe(Ш) groups comparing with the control group. In addition, Fe(Ш) inhibited the genes related to the generation of electron carriers, NADH and FADH2, in TCA cycle and glycolysis processes, which could result in a lower carbon utilization efficiency for microbial denitrification.

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Iron deposits in cells and tissues can be detected by ex vivo histological examination through the Prussian blue (PB) staining. This practical, inexpensive, and highly sensitive technique involves the treatment of fixed tissue sections and cells with acid solutions of ferrocyanides that combine with ferric ion forming a bright blue pigment (i.e., ferric ferrocyanide). The staining can be applied to visualize iron oxide nanoparticles (IONPs), versatile magnetic nanosystems that are used in various biomedical applications and whose localization is usually required at a higher resolution than that enabled by in vivo tracking techniques.

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It is well known the capacity of potassium ferrate (Fe(VI)) for the oxidation of pollutants or co-precipitation and adsorption of hazardous species. However, little information has been paid on the adsorption and co-precipitation contribution of the Fe(VI) resultant nanoparticles, the in situ hydrolytic ferric iron oxides. Here, the removal of arsenate (As(V)) and arsenite (As(III)) by Fe(VI) was investigated, which focused on the interaction mechanisms of Fe(VI) with arsenic, especially in the contribution of the co-precipitation and adsorption of its hydrolytic ferric iron oxides. pH and Fe(VI) played significant roles on arsenic removal; over 97.8% and 98.1% of As(V) and As(III) removal were observed when Fe(VI):As(V) and Fe(VI):As(III) were 24:1 and 16:1 at pH 4, respectively. The removal of As(V) and As(III) by in situ and ex situ formed hydrolytic ferric iron oxides was examined respectively. The results revealed that As(III) was oxidized by Fe(VI) to As(V), and then was removed though co-precipitation and adsorption by the hydrolytic ferric iron oxides with the contribution content was about 1:3. For As(V), it could be removed directly by the in situ formed particles from Fe(VI) through co-precipitation and adsorption with the contribution content was about 1:1.5. By comparison, As(III) and As(V) were mainly removed through adsorption by the 30-min hydrolytic ferric iron oxides during the ex situ process. The hydrolytic ferric iron oxides size was obviously different in the process of in situ and ex situ, possessing abundant and multiple morphological structures ferric oxides, which was conducive for the efficient removal of arsenic. This study would provide a new perspective for understanding the potential of Fe(VI) treatment on arsenic control.

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The influence of mineralogy on the assembly of microbial communities in glacial environments has been difficult to assess due to complications in isolating mineralogy from other variables. Here we assess the abundance and composition of microbial communities that colonized defined minerals incubated for 12 months in two meltwater streams (N and S) emanating from Kaldalónsjökull (Kal), a basalt-hosted glacier in Iceland. The two streams shared similar meltwater geochemistry as well as bedrock and proglacial sediment elemental compositions. Yet genomic DNA and PCR-amplifiable 16S rRNA genes were detected only in Kal S. The amount of recoverable DNA was highest for hematite incubated in Kal S and the composition of 16S rRNA genes recovered from Kal S sediments was most like those recovered from hematite and magnetite, an effect driven largely by similarities in the relative abundance of the putative hydrogenotrophic iron reducer Rhodoferax. We suggest this is attributable to comminution and weathering reactions involving exposed iron silicate minerals that generate and release hydrogen and Fe(III) that can be coupled to support microbial metabolism in Kaldalónsjökull, and possibly other basaltic habitats. The low abundance of cells in Kal N could be due to low availability of Fe(III) or another substrate.

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Background: Ceruloplasmin plays an important role in the regulation of iron metabolism. Ceruloplasmin is an acute-phase protein known to have many metabolic effects. Its activity increases during infection, inflammation, and compensation of oxidation. In the current study, our aim is to develop a new method for the measurement of ferroxidase activity without requiring any chromogen. Methods: Venous blood samples were collected into serum separator tubes. Ferric iron ions formed by the enzyme ferroxidase were measured, both manually and fully automatically, at the 415 nm wavelength without using chromogen. These results were compared to conventional ferroxidase measurement methods and to the immunoturbidimetric ceruloplasmin measurement method. Results: The detection limit of the new assay was 14.8 U/L. The upper limit of the linearity was 1380 U/L. Precision values were calculated for high, medium, and low levels of ferroxidase activity in serum pool. The coefficient of variation was <5% for each level. Conclusion: In the present method, chromogens are not used. With its considerably low cost and short reaction time, this method is able to provide fast results, can be performed easily, and makes accurate measurements.