The Waelz Slag from Electric Arc Furnace Dust Processing: Characterization and Magnetic Separation Studies.

The Waelz slag generated during electric arc furnace dust processing is an iron-rich product with significant amounts of iron, zinc and copper. About 600-800 kg of the Waelz slag is generated per ton of the dust processed. The Waelz slag samples from two different plants were thoroughly characterized using inductively coupled plasma optical emission spectroscopy (ICP-AES), X-ray diffraction analysis (XRD), chemical phase analysis, Mössbauer spectroscopy and other supporting methods. The phase distribution of iron, zinc and copper was determined in the Waelz slag samples. Low-intensity wet magnetic separation was tested for the iron recovery from the Waelz slag samples. It was found that the Waelz slag samples have complex chemical and mineralogical compositions, which can impede the selective recovery of valuable elements. The obtained results indicate that the chemical and mineralogical composition of the Waelz slag samples has a considerable effect on the magnetic separation indexes. The experiments showed that the iron concentrates with Fe contents of 73% and 46.8% with the metallization degrees of 87.2% and 57.5% and the iron recovery degree of 54.8% and 52.9% were obtained at optimal conditions for two different samples, respectively, without selective segregation of Cu and Zn in the magnetic or non-magnetic fraction.

Bulk ferromagnetism in cleavable van der Waals telluride NbFeTe2.

A van der Waals telluride, NbFeTe2, has been synthesized using chemical vapor transport reactions. The optimized synthetic conditions yield high-quality single crystals with a novel monoclinic crystal structure. Monoclinic NbFeTe2 demonstrates a (100) cleavage plane, bulk ferromagnetism below 87 K, and a metallic ground state-the necessary prerequisites for needed spintronics technologies.

Dramatic change in the properties of magnetite-modified MOF particles depending on the synthesis approach.

Iron-containing metal-organic frameworks are promising Fenton catalysts. However, the absence of additional modifiers has proven difficult due to the low reaction rates and the inability to manipulate the catalysts. We hypothesize that the production of iron oxide NPs in the presence of a metal-organic framework will increase the rate of the Fenton reaction and lead to the production of particles that can be magnetically manipulated without changing the structure of the components. A comprehensive approach lead to a metal organic framework using the example of MIL-88b (Materials of Institute Lavoisier) modified with iron oxides NPs: formulation of iron oxide in the presence of MIL-88b and vice versa. The synthesis of MIL-88b consists of preparing a complexation compound with the respective structure and addition of terephthalic acid. The synthesis of MIL-88b facilitates to control the topology of the resulting material. Both methods for composite formulation lead to the preservation of the structure of iron oxide, however, a more technologically complex approach to obtaining MIL-88b in the presence of Fe3O4 suddenly turned out to be the more efficient for the release of iron ions.

Low-Temperature Treatment of Boehmitic Bauxite Using the Bayer Reductive Method with the Formation of High-Iron Magnetite Concentrate.

The Bayer process is the main method of alumina production worldwide. The use of low-quality bauxites for alumina production results in the formation of a significant amount of technogenic waste-bauxite residue (BR). The Bayer reductive method is one possible way to eliminate BR stockpiling, but it requires high-pressure leaching at temperatures higher than 220 °C. In this research, the possibility of boehmitic bauxite atmospheric pressure leaching at both the first and second stages or high-pressure leaching at the second stage with the simultaneous reduction of hematite to magnetite was investigated. Bauxite and solid residue after NaOH leaching were characterized using XRD, SEM-EDS, and Mössbauer spectroscopy methods. The first stage of leaching under atmospheric pressure with the addition of Fe(II) species in a strong alkali solution (330-400 g L-1 Na2O) resulted in a partial reduction of the iron minerals and an extraction of more than 60% of Si and 5-25% of Al (depending on caustic modulus of solution) after 1 h. The obtained desilicated bauxite was subjected to atmospheric leaching at 120 °C in a strong alkali solution (350 g L-1) or high-pressure leaching at 160-220 °C using the Bayer process mother liquor in order to obtain a concentrate with a magnetite content higher than 83 wt. %.

Functionalized Magnetite Nanoparticles: Characterization, Bioeffects, and Role of Reactive Oxygen Species in Unicellular and Enzymatic Systems.

The current study evaluates the role of reactive oxygen species (ROS) in bioeffects of magnetite nanoparticles (MNPs), such as bare (Fe3O4), humic acids (Fe3O4-HA), and 3-aminopropyltriethoxysilane (Fe3O4-APTES) modified MNPs. Mössbauer spectroscopy was used to identify the local surrounding for Fe atom/ions and the depth of modification for MNPs. It was found that the Fe3O4-HA MNPs contain the smallest, whereas the Fe3O4-APTES MNPs contain the largest amount of Fe2+ ions. Bioluminescent cellular and enzymatic assays were applied to monitor the toxicity and anti-(pro-)oxidant activity of MNPs. The contents of ROS were determined by a chemiluminescence luminol assay evaluating the correlations with toxicity/anti-(pro-)oxidant coefficients. Toxic effects of modified MNPs were found at higher concentrations (>10−2 g/L); they were related to ROS storage in bacterial suspensions. MNPs stimulated ROS production by the bacteria in a wide concentration range (10−15−1 g/L). Under the conditions of model oxidative stress and higher concentrations of MNPs (>10−4 g/L), the bacterial bioassay revealed prooxidant activity of all three MNP types, with corresponding decay of ROS content. Bioluminescence enzymatic assay did not show any sensitivity to MNPs, with negligible change in ROS content. The results clearly indicate that cell-membrane processes are responsible for the bioeffects and bacterial ROS generation, confirming the ferroptosis phenomenon based on iron-initiated cell-membrane lipid peroxidation.

High-Iron Bauxite Residue (Red Mud) Valorization Using Hydrochemical Conversion of Goethite to Magnetite.

Bauxite residue (BR), also known as red mud, is a byproduct of the alumina production using the Bayer process. This material is not used to make iron or other iron-containing products worldwide, owing to its high content of sodium oxide and other impurities. In this study, we investigated the hydrochemical conversion of goethite (FeOOH) to magnetite (Fe3O4) in high-iron BR from the Friguia alumina refinery (Guinea) by Fe2+ ions in highly concentrated alkaline media. The simultaneous extraction of Al and Na made it possible to obtain a product containing more than 96% Fe3O4. The results show that the magnetization of Al-goethite and Al-hematite accelerates the dissolution of the Al from the iron mineral solid matrix and from the desilication product (DSP). After ferrous sulfate (FeSO4·7H2O) was added directly at an FeO:Fe2O3 molar ratio of 1:1 at 120 °C for 150 min in solution with the 360 g L-1 Na2O concentration, the alumina extraction ratio reached 96.27% for the coarse bauxite residue size fraction (Sands) and 87.06% for fine BR obtained from red mud. The grade of iron (total iron in the form of iron elements) in the residue can be increased to 69.55% for sands and 58.31% for BR. The solid residues obtained after leaching were studied by XRD, XRF, TG-DTA, VSM, Mössbauer spectroscopy, and SEM to evaluate the conversion and leaching mechanisms, as well as the recovery ratio of Al from various minerals. The iron-rich residues can be used in the steel industry or as a pigment.

Uplink NOMA-MIMO Systems with Rayleigh Power Distribution.

The article is devoted to multiple-input multiple-output antenna systems, also called MIMO systems, which are widely used in wireless communication systems. In this article we consider a case when the MIMO system works in overloaded mode. In this mode MIMO systems can be considered as a system with non-orthogonal multiple access NOMA. The main goal of this article is to analyze this interesting case using statistical computer simulation. Based on the analysis of the capacity of a discrete-continuous multiuser MIMO uplink channel, the possibility of such systems functioning in overload mode is proved.

Comprehensive Study on the Mechanism of Sulfating Roasting of Zinc Plant Residue with Iron Sulfates.

Zinc plant residue (ZPR) is a secondary material generated during hydrometallurgical zinc production that contains considerable contents of valuable elements such as Zn, Cu, Fe, Pb, Cd, Ag, In, Ga, Tl. Zinc, copper and accompanying elements in ZPR are in different minerals, mainly in the ferrites. A promising approach for recycling ZPR is the sulfating roasting using iron sulfates followed by water leaching. In this study, the composition of ZPR and the obtained products were thoroughly investigated by various methods including X-ray diffraction analysis (XRD), chemical phase analysis and Mössbauer spectroscopy. The effect of temperature, amount of iron sulfates and roasting time on the conversion of valuable metals into a water-soluble form was thermodynamically and experimentally studied both using pure ferrites and ZPR. Based on the results of time-resolved XRD analysis and synchronous thermal analysis (STA), a mechanism of the sulfation roasting was elucidated. The rate-controlling step of zinc and copper sulfation process during the ZPR roasting was estimated. The sulfating roasting at 600 °C during 180 min with the optimal Fe2(SO4)3∙9H2O addition followed by water leaching enables to recover 99% Zn and 80.3% Cu, while Fe, Pb, Ag, In, Ga retained almost fully in the residue.

Common and rare iron, sulfur, and zinc minerals in technogenically contaminated hydromorphic soil from Southern Russia.

Soils formed after the desiccation of Lake Atamanskoe, which has served as a reservoir for liquid industrial waste from the city of Kamensk-Shakhtinsky during a long time, were studied. These soils differ from zonal soils by a strong contamination with zinc and sulfur. Preliminary studies showed that Fe compounds fix a significant part of zinc. This requires to study S, Zn, and Fe minerals. In this work, Mössbauer spectroscopy was used for the identification of iron compounds and scanning electron microscopy was used for the microanalysis of these and other minerals. To facilitate the identification of Fe minerals, brown iron ocher was removed from a contaminated soil sample and analyzed. From electron microscopy and Mössbauer spectroscopy data, ocher contained hydrogoethite with a high content of sorption water and schwertmannite (a rare mineral, probably found in Russia for the first time). The chemical composition of this schwertmannite better corresponds to the Cashion-Murad model than to the Bigham model. Particles of partially oxidized magnetite and wustite enriched with zinc were revealed under electron microscope. Siderite with partial substitution of Fe2+ by Zn2+ was detected. Thus, contaminated hydromorphic soil contains both common minerals (illite, goethite, hematite, gypsum) and rare minerals (schwertmannite, Zn siderite, partially oxidized magnetite and wustite enriched with zinc).

Eco-Friendly Iron-Humic Nanofertilizers Synthesis for the Prevention of Iron Chlorosis in Soybean (Glycine max) Grown in Calcareous Soil.

Iron deficiency is a frequent problem for many crops, particularly in calcareous soils and iron humates are commonly applied in the Mediterranean basin in spite of their lesser efficiency than iron synthetic chelates. Development and application of new fertilizers using nanotechnology are one of the potentially effective options of enhancing the iron humates, according to the sustainable agriculture. Particle size, pH, and kinetics constrain the iron humate efficiency. Thus, it is relevant to understand the iron humate mechanism in the plant-soil system linking their particle size, characterization and iron distribution in plant and soil using 57Fe as a tracer tool. Three hybrid nanomaterials (F, S, and M) were synthesized as iron-humic nanofertilizers (57Fe-NFs) from leonardite potassium humate and 57Fe used in the form of 57Fe(NO3)3 or 57Fe2(SO4)3. They were characterized using Mössbauer spectroscopy, X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS), transmission electron microscopy (TEM) and tested for iron availability in a calcareous soil pot experiment carried out under growth chamber conditions. Three doses (35, 75, and 150 µmol pot-1) of each iron-humic material were applied to soybean iron deficient plants and their iron nutrition contributions were compared to 57FeEDDHA and leonardite potassium humate as control treatments. Ferrihydrite was detected as the main structure of all three 57Fe-NFs and the plants tested with iron-humic compounds exhibited continuous long-term statistically reproducible iron uptake and showed high shoot fresh weight. Moreover, the 57Fe from the humic nanofertilizers remained available in soil and was detected in soybean pods. The Fe-NFs offers a natural, low cost and environmental option to the traditional iron fertilization in calcareous soils.

Key Roles of Size and Crystallinity of Nanosized Iron Hydr(oxides) Stabilized by Humic Substances in Iron Bioavailability to Plants.

Availability of Fe in soil to plants is closely related to the presence of humic substances (HS). Still, the systematic data on applicability of iron-based nanomaterials stabilized with HS as a source for plant nutrition are missing. The goal of our study was to establish a connection between properties of iron-based materials stabilized by HS and their bioavailability to plants. We have prepared two samples of leonardite HS-stabilized iron-based materials with substantially different properties using the reported protocols and studied their physical chemical state in relation to iron uptake and other biological effects. We used Mössbauer spectroscopy, XRD, SAXS, and TEM to conclude on iron speciation, size, and crystallinity. One material (Fe-HA) consisted of polynuclear iron(III) (hydr)oxide complexes, so-called ferric polymers, distributed in HS matrix. These complexes are composed of predominantly amorphous small-size components (<5 nm) with inclusions of larger crystalline particles (the mean size of (11 ± 4) nm). The other material was composed of well-crystalline feroxyhyte (δ'-FeOOH) NPs with mean transverse sizes of (35 ± 20) nm stabilized by small amounts of HS. Bioavailability studies were conducted on wheat plants under conditions of iron deficiency. The uptake studies have shown that small and amorphous ferric polymers were readily translocated into the leaves on the level of Fe-EDTA, whereas relatively large and crystalline feroxyhyte NPs were mostly sorbed on the roots. The obtained data are consistent with the size exclusion limits of cell wall pores (5-20 nm). Both samples demonstrated distinct beneficial effects with respect to photosynthetic activity and lipid biosynthesis. The obtained results might be of use for production of iron-based nanomaterials stabilized by HS with the tailored iron availability to plants. They can be applied as the only source for iron nutrition as well as in combination with the other elements, for example, for industrial production of "nanofortified" macrofertilizers (NPK).