Search Results (266)

Microminerals such as cobalt (Co), copper (Cu), iodine (I), iron (Fe), manganese (Mn), molybdenum (Mo), selenium (Se), and zinc (Zn) play key roles in cattle health. However, trace element imbalances are often underdiagnosed. This study retrospectively analyzed serum samples from 1273 cows across 117 herds in Spain, encompassing conventional dairy (n = 46), pasture-based dairy (n = 11), organic dairy (n = 25), and semi-extensive beef (n = 35) systems. Trace elements were determined by inductively coupled plasma mass spectrometry (ICP-MS). All herds were investigated for clinical or productive issues where mineral deficiencies were suspected. Significant differences were found in serum trace mineral concentrations between production systems. Adequacy rates were highest in conventional dairy herds receiving routine mineral supplementation, while deficiencies in Se, I, and Cu were frequently detected in pasture-based, organic, and beef herds. Zinc deficiencies were rare and typically involved complex, combined deficiencies. At the farm level, multielement deficiencies (≥3 elements) were detected in 39–45% of organic, pasture-based, and beef herds, but in only 5% of conventional dairy herds (p < 0.001). Principal component and cluster analyses produced consistent groupings of minerals according to dietary supplementation and soil-driven exposure. These findings highlight the increased vulnerability of low-input systems to complex micromineral imbalances and underline the importance of system-adapted mineral-monitoring and supplementation strategies in herd health management. However, as the study is based on diagnostic submissions rather than a randomized herd survey, the findings should be interpreted with caution due to potential selection bias. Full article

In some cases, the catalytic processes involve the formation of self-organized supramolecular structures due to H-bonds and other non-covalent interactions. It has been suggested that the construction of self-assembled catalytic systems is a promising strategy to mimic enzyme catalysis at the model level. As a rule, the real catalysts are not the primary catalytic complexes, but rather, those that are formed during the catalytic process. In our earlier works, we have established that the effective catalysts M(II)_xL¹_y(L¹_ox)_z(L²)_n(H₂O)_m (M = Ni, Fe, L¹ = acac⁻, L² = activating electron-donating ligand) for the selective oxidation of ethylbenzene to α-phenyl ethyl hydroperoxide are the result of the transformation of primary (Ni(Fe)L¹)_x(L²)_y complexes during the oxidation of ethylbenzene. In addition, the mechanism of the transformation to active complexes is similar to the mechanism of action of NiFeARD (NiFe-acireductone dioxygenase). Based on kinetic and spectrophotometric data, we hypothesized that the high stability of effective catalytically active complexes may be associated with the formation of stable supramolecular structures due to intermolecular hydrogen bonds and possibly other non-covalent bonds. We confirmed this assumption using AFM. In this work, using AFM, we studied the possibility of forming supramolecular structures based on iron complexes with L²-crown ethers and quaternary ammonium salts, which are catalysts for the oxidation of ethylbenzene and are models of FeARD (Fe-acireductone dioxygenase). The formation of supramolecular structures based on complexes of natural Hemin with PhOH and L-histidine or Hemin with L-tyrosine and L-histidine, which are models of heme-dependent tyrosine hydroxylase and cytochrome P450-dependent monooxygenases (AFM method), may indicate the importance of outer-sphere regulatory interactions with the participation of Tyrosine and Histidine in the mechanism of action of these enzymes. Full article

Efforts have been underway worldwide to reintroduce seawater to many historically diked salt marshes for restoration of tidal flow and associated estuarine habitat. Seawater restoration to a diked Cape Cod marsh was simulated using the computer program PHREEQC based on previously conducted microcosm experiments to better understand the associated timing and sequence of multiple biogeochemical reactions and their implications to aquatic health. Model simulations show that acidic, reducing waters with high concentrations of sorbed ferrous iron (Fe[II]), aluminum (Al), sulfide (S²⁻), ammonia (NH₄⁺ + NH₃), and phosphate (PO₄³⁻) are released through desorption and sediment weathering following salination that can disrupt aquatic habitat. Models were developed for one-dimensional reactive transport of solutes in diked, flooded (DF) marsh sediments and subaerially exposed, diked, drained (DD) sediments by curve matching porewater solute concentrations and adjusting the sedimentary organic matter (SOM) degradation rates based on the timing and magnitude of Fe(II) and S²⁻ concentrations. Simulated salination of the DD sediments, in particular, showed a large release of Al, Fe(II), NH₄⁺, and PO₄³⁻; the redox shift to reductive dissolution provided higher rates of SOM oxidation. The sediment type, iron source, and seasonal timing associated with seawater restoration can affect the chemical speciation and toxicity of constituents to aquatic habitat. The constituents of concern and their associated complex biogeochemical reactions simulated in this study are directly relevant to the increasingly common coastal marsh salination, either through tidal restoration or rising sea level. Full article

Biochar, a porous carbonaceous material derived from the pyrolysis of biomass under oxygen-limited conditions, offers several advantages for environmental remediation, including a high specific surface area, ease of preparation, and abundant raw material sources. However, the application of pristine biochar is limited by its inherent physicochemical shortcomings, such as a lack of active functional groups and limited elemental compositions. To overcome these limitations, metal-modified biochars have garnered increasing attention. In particular, iron-manganese (Fe-Mn) modification significantly enhances the adsorption capacity, redox potential, and microbial activity of biochar, owing to the synergistic interactions between Fe and Mn. Iron-manganese-modified biochar (FM-BC) has demonstrated effective removal of heavy metals, organic matter, phosphate, and nitrate through mechanisms including mesoporous adsorption, redox reactions, complexation, electrostatic interactions, and precipitation. Moreover, FM-BC can improve soil physicochemical properties and support plant growth, highlighting its promising potential for broader environmental application. This review summarizes the preparation methods, environmental remediation mechanisms, and practical applications of FM-BC and discusses future directions in mechanism elucidation, biomass selection, and engineering implementation. Overall, FM-BC, with its tunable properties and multifunctional capabilities, emerges as a promising and efficient material for addressing complex environmental pollution challenges. Full article

Acinetobacter baumannii is listed by the World Health Organization as an emerging bacterial priority pathogen, the prevalence and multidrug resistance of which have been increasing. This functional genomics study aimed to understand the drug-resistance mechanisms of an extensively drug-resistant (XDR) A. baumannii strain (IRMCBCU95U) isolated from a transtracheal aspirate sample from a female patient with end-stage renal disease in Saudi Arabia. The whole genome of IRMCBCU95U (4.3 Mbp) was sequenced using Oxford Nanopore long-read sequencing to identify and compare the antibiotic-resistance profile and genomic features of A. baumannii IRMCBCU95U. The antibiogram of A. baumannii IRMCBCU95U revealed resistance to multiple antibiotics, including cefepime, ceftazidime, ciprofloxacin, imipenem, meropenem and piperacillin/tazobactam. A comparative genomic analysis between IRMCBCU95U and A. baumannii K09-14 and ATCC 19606 identified significant genetic heterogeneity and mosaicism among the strains. This analysis also demonstrated the hybrid nature of the genome of IRMCBCU95U and indicates that horizontal gene transfer may have occurred between these strains. The IRMCBCU95U genome has a diverse range of genes associated with antimicrobial resistance and mobile genetic elements (ISAba1 and IS26) associated with the spread of multidrug resistance. The presence of virulence-associated genes that are linked to iron acquisition, motility and transcriptional regulation confirmed that IRMCBCU95U is a priority human pathogen. The plasmid fragment IncFIB(pNDM-Mar) observed in the strain is homologous to the plasmid in Klebsiella pneumoniae (439 bp; similarity: 99.09%), which supports its antimicrobial resistance. From these observations, it can be concluded that the clinical A. baumannii IRMCBCU95U isolate is an emerging extensively drug-resistant human pathogen with a novel combination of resistance genes and a plasmid fragment. The complex resistome of IRMCBCU95U highlights the urgent need for genomic surveillance in hospital settings in Saudi Arabia to fight against the spread of extensively drug-resistant A. baumannii. Full article

The interactions between iron oxides and organic carbon within the particulate organic matter (POM) and mineral-associated organic matter (MAOM) fractions in paddy soils remain insufficiently understood, yet they are likely crucial for unlocking the carbon sequestration potential of these systems. In this study, we investigated the distribution of soil iron oxides and organic carbon within POM and MAOM fractions following 10 years of continuous irrigation and organic amendment management. We also examined the relationship between iron oxide transformation and these two SOC (soil organic carbon) fractions. Our results demonstrated that, under both flooded irrigation and controlled irrigation regimes, straw return or manure application effectively enhanced soil carbon sequestration, as evidenced by increases in both POM-C (POM-associated organic carbon) and MAOM-C (MAOM-associated organic carbon) contents. Meanwhile, exogenous carbon inputs promoted the transformation of crystalline iron oxides into short-range ordered iron oxides and iron oxide colloids, thereby enhancing the activation and complexation degree of soil iron oxides and facilitating the formation of Fe-bound organic carbon. Further regression analysis revealed that the activation degree of iron oxides had a stronger influence on POM-C, whereas the complexation degree had a greater effect on MAOM-C. This implies that exogenous carbon inputs are effective in promoting soil carbon sequestration in both flooded and water-saving irrigated rice paddies and that iron oxide transformation plays a key role in mediating this effect. Full article

Current biodiesel production is costly, in part due to the catalysts added during transesterification and later washed out. We have previously shown that intact rapeseed shells can be ball-milled with an alcohol to produce biodiesel without an added catalyst. Here, we report on the activation and identity of the complexing agent within the shells of rapeseeds and sunflower seeds. Lignin, present in the cell walls of plant matter, complexes with iron and manganese within metallic media, such as in a ball mill, and acts as a catalyst support in a transesterification reaction with oil and methanol. When ball-milled with methanol, rapeseed and sunflower seeds produce up to 90% biodiesel, similar to yields produced by industrial methods. However, this new method for producing biodiesel is a greener alternative, as it requires fewer organic solvents, may reduce the time and energy required for synthesis, and may reduce the effort required for product purification. Full article

Heterogeneous electro-Fenton (HEF) technology utilizing iron-based cathode catalysts has emerged as an efficient advanced oxidation process for wastewater treatment, demonstrating outstanding performance in degrading emerging organic contaminants (EOCs) while maintaining environmental sustainability. The performance of this technology is governed by two critical processes: the accumulation of H₂O₂ and the electron transfer mechanisms governing the Fe(III)/Fe(II) redox cycle. This review comprehensively summarizes recent advances in understanding the electron transfer mechanisms in iron-based HEF systems and their applications for EOC degradation. Five representative catalyst categories are critically analyzed, including zero-valent iron/alloys, iron oxides, iron-carbon/nitrogen-doped carbon composites, iron sulfides/phosphides, and iron-based MOFs, with a particular focus on their structural design, catalytic performance, and electron transfer mechanisms. A particular focus is placed on strategies enhancing Fe(III)/Fe(II) cycling efficiency and the interplay between radical (^•OH) and non-radical (¹O₂) oxidation pathways, including their synergistic effects in complex wastewater systems. Major challenges, including catalyst stability, pH adaptability, and selective oxidation in complex matrices, are further discussed. Potential solutions to these limitations are also discussed. This review provides fundamental insights for designing high-efficiency iron-based HEF catalysts and outlines future research directions to advance practical applications. Full article

The tequila industry faces several environmental challenges due to its high yields of contaminants, especially tequila distillation stillage or tequila vinasses, with ten to twelve liters produced per liter of tequila. All treatments aim to shorten retention times to avoid the need for large equipment or new facilities and the saturation of residues within tequila distilleries. The complexity of tequila vinasses has led to treatments with several stages, whereby most of the organic matter content is reduced, but the treatment range results are insufficient. This study aimed to evaluate a fourth-stage tequila vinasse treatment using an electrocoagulation system that uses inexpensive electrodes (SS cathodes and iron anodes), has a low electrical consumption, and applies low voltages in order to meet safety, economic, and environmental criteria so as to comply with Mexican norm NOM-001-SEMARNAT-2021. Three sets of voltage–amperage controllable power source, a 4 mm cylindrical 304 stainless-steel cathode, and a 9 mm iron anode with 200 mL samples in 250 mL beakers were used; three replicas (R1, R2, and R3) underwent 2 h treatment at 1–6 volts to evaluate the voltage effect and 1–6 h of 5-volt treatment to assess the time effect. All samples were filtered with 8 μm and 0.25 μm meshes. Chemical oxygen demand, pH, electrical conductivity, turbidity, and color measurements (SAC for λ 436, 525, and 620 nm) were taken. The experiments determined the optimal voltage and time, considering a hydraulic retention time below 6 h. The results show that electrocoagulation of pretreated tequila vinasses effectively helps in the final removal of organic matter measured as COD, reaching values below 150 COD mg/L at 5–6 h with 5 V treatments and color reduction with 5 V, 1 h treatment. This leads to final polishing that complies with the Mexican wastewater discharge norm criteria. Full article

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a promising alternative. Although they have a lower output potential compared to hydrogen fuel cells, peroxide can act as both the oxidizing and reducing agent, simplifying the structure of the cell. In addition to reducing the complexity, hydrogen peroxide is stable in liquid form and can be stored in less demanding methods. This paper investigates chelated metals as electrode material for hydrogen peroxide fuel cells. Chelated metal complexes are ring-like structures that form from binding organic or inorganic compounds with metal ions. They are used in medical imaging, water treatment, and as catalysts for reactions. Copper(II) phthalocyanine, phthalocyanine green, poly(copper phthalocyanine), bis(ethylenediamine)copper(II) hydroxide, iron(III) ferrocyanine, graphene oxide decorated with Fe₃O₄, zinc phthalocyanine, magnesium phthalocyanine, manganese(II) phthalocyanine, cobalt(II) phthalocyanine are investigated as electrode materials for peroxide fuel cells. In this study, the performance of these materials is evaluated using cyclic voltammetry. The voltammograms are compared, as well as observations are made during the materials’ use to measure their effectiveness as electrode material. There has been limited research comparing the use of these chelated metals in the context of hydrogen peroxide fuel cells. Through this research, the goal is to further the viability of hydrogen peroxide fuel cells. Poly(copper phthalocyanine) and graphene oxide doped with iron oxides had strong redox catalytic activity for use in acidic peroxide single-compartment fuel cells, where the poly(copper phthalocyanine) electrode compound generated the highest peak power density of 7.92 mW/cm² and cell output potential of 0.634 V. Full article

Soil barrenness and a poor stability of organic carbon are important factors restricting sustainable agricultural development. The effects of straw incorporation and nitrogen (N) fertilization on soil aggregates, soil organic carbon (SOC) functional groups, iron (Fe) oxides, and SOC sequestration were evaluated in saline–alkali soil. In this study, we established six treatments involving the combined addition of straw and N in saline–alkali soil in the Yellow River Delta, China, to investigate the changes in SOC. A field experiment was conducted with two N levels (N1, 270 kg N ha⁻¹; N2, 210 kg N ha⁻¹) and three C treatments (S0, 0 kg ha⁻¹; S1, 5000 kg ha⁻¹; S2, 10,000 kg ha⁻¹). Compared with S0 treatments, straw incorporation and N application significantly increased the proportion of small macro-aggregates, and the mean weight diameter (MWD) was increased by 8.3–18.6%. Under the N2 treatment, with an increase in straw incorporation, the contents of organically complexed Fe oxides (Fep), especially small macro-aggregates and micro-aggregates, increased significantly. Meanwhile, polysaccharides-C and aromatic-C were mainly distributed in small macro-aggregates, forming aromatic Fe complexes with Fep and remaining at the aggregate interface. Compared with the N1S0 treatment, SOC storage increased by 3.94% and 5.12% in the N2S1 and N2S2 treatments, respectively. This could primarily be attributed to an improvement in soil structure, the optimization of OC functional group composition, and the formation of organo-Fe complexes. Straw incorporation and N application were optimal management measures and improved C stability and sequestration capacity. A halved straw incorporation and a reduced N application were the best treatment options for saline–alkali soil. Full article

This study assesses iron–carbon micro-electrolysis coupled with hydrogen peroxide for removing organic pollutants from secondary sedimentation tank effluent. Gas chromatography–mass spectrometry (GC-MS) analysis identified 11 major pollutants, with thiophene and palmitic acid being predominant, contributing significantly to the chemical oxygen demand (COD) due to their stability and molecular sizes. Iron–carbon micro-electrolysis showed notable degradation of thiophene and indole, though it was less effective for other organics. The combined process enhanced the degradation efficiency, hydrolyzing >85% of esters into less toxic alcohols, yet palmitic acid remained largely undegraded. The combined treatment process (influent pH 3.5, H₂O₂ dose 170 mg/L) improved degradation, converting most esters to alcohols and reducing environmental impacts, yet palmitic acid remained largely undegraded. A 35-day pilot test under optimal conditions achieved an average COD removal rate of 57%. The study concludes that the combined process has potential for complex pollutant degradation but requires further optimization for better efficiency. Full article

Rhizobial bacteria perform a number of extremely important functions in the soil environment. In addition to fixing molecular nitrogen and transforming it into a form available to plants, they participate in the circulation of elements and the decomposition of complex compounds present in the soil, sometimes toxic to other organisms. This review article describes the molecular mechanisms occurring in the most diverse group of rhizobia, the genus Bradyrhizobium, allowing these bacteria to adapt to selected substances found in the soil. Firstly, the adaptation of bradyrhizobia to low and high concentrations of elements such as iron, phosphorus, sulfur, calcium and manganese was shown. Secondly, the processes activated in their cells in the presence of heavy metals such as lead, mercury and arsenic, as well as radionuclides, were described. Additionally, due to the potential use of Bradyrhziobium as biofertilizers, their response to pesticides commonly used in agriculture, such as glyphosate, sulfentrazone, chlorophenoxy herbicides, flumioxazine, imidazolinone, atrazine, and insecticides and fungicides, was also discussed. The paper shows the great genetic diversity of bradyrhizobia in terms of adapting to variable environmental conditions present in the soil. Full article

Metallosurfactants combine the unique soft-matter properties of surfactants with magnetic functionalities of metal ions. The inclusion of iron-based species, in particular, can further boost the functionality of the material, owing to iron’s ability to adopt multiple oxidation states and form both high-spin and low-spin complexes. Motivated by this, a series of hybrid inorganic-organic dodecylpyridinium metallosurfactants with iron-containing counterions was developed. It was established that using either divalent or trivalent iron halides in a straightforward synthetic procedure yields C₁₂Py-metallosurfactants with distinct complex counterions: (C₁₂Py)₂[Fe₂X₆O] and (C₁₂Py)[FeX₄] (X = Cl or Br), respectively. A combination of techniques—including conductometry, dynamic and electrophoretic light scattering, single-crystal and thermogravimetric analysis, and magnetic measurements—provided in-depth insights into their solution and solid-state properties. The presence of different iron-based counterions significantly influences the crystal structure (interdigitated vs. non-interdigitated bilayers), magnetic properties (paramagnetic vs. nonmagnetic singlet ground state), and self-assembly (vesicles vs. micelles) of the dodecylpyridinium series. To our knowledge, this is the first report on the synthesis and characterization of hybrid organic-inorganic metallosurfactants containing the μ-oxo-hexahalo-diferrate anion. Full article