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The existence of toxic and carcinogenic pentavalent antimony in water is a great safety problem. In order to remove antimony(V) from water, the purpose of this study was to prepare a novel graphene nano iron zinc (rGO/NZV-FeZn) photocatalyst via hydrothermal method followed by ultrasonication. Herein, weakly magnetic nano-Fe–Zn materials (NZV-FeZn, GACSP/NZV-FeZn, and rGO/NZV-FeZn) capable of rapid and efficient Sb(V) adsorption from water were prepared and characterised. In particular, rGO/NZV-FeZn was shown to comprise franklinite, Fe0, and graphite. Adsorption data were fitted by a quasi-second-order kinetic equation and Langmuir model, revealing that among these materials, NZV-FeZn exhibited the best Sb removal performance (543.9 mgSb gNZV-FeZn−1, R2 = 0.951). In a practical decontamination test, Sb removal efficiency of 99.38% was obtained for a reaction column filled with 3.5 g of rGO/NZV-FeZn. Column regenerability was tested at an initial concentration of 0.8111 mgSb L−1, and the treated water obtained after five consecutive runs complied with the GB5749-2006 requirement for Sb. rGO/NZV-FeZn was suggested to remove Sb(V) through adsorption-photocatalytic reduction and flocculation sedimentation mechanisms and, in view of its high cost performance, stability, and upscalable synthesis, was concluded to hold great promise for source water and wastewater treatment.

In this work, Fe3O4@ZnFe2O4 core/shell nanoparticles were obtained by depositing ZnO by the wet chemistry method on the surface of Fe3O4 nanoparticles seeds obtained by the chemical bath deposition method. Fe3O4 and Fe3O4@ZnFe2O4 were characterized by Field Emission Scanning Electron Microscopy, Energy Dispersive X-ray Spectrometry, Transmission Electron Microscopy, X-ray Diffraction, Ultraviolet–Visible Spectroscopy, Diffuse Reflectance, and Fourier Transformed Infrared Spectroscopy (FTIR). The Fe3O4@ZnFe2O4 nanoparticles formed an urchin-like spheres morphology (corresponding to Fe3O4) with a homogeneous shell of ZnFe2O4. XRD analysis showed a magnetite crystal structure for Fe3O4 and a franklinite (ZnFe2O4) crystal structure for the shell. Fe3O4@ZnFe2O4 showed higher crystallinity when applying a heat treatment, showing a crystal size of 9.12 nm with heat treatment and 9.43 nm without heat treatment. The diffuse reflectance results suggested an indirect band gap of 1.85 eV for Fe3O4 and two indirect band gaps of 1.85 eV and 2.54 eV for Fe3O4@ZnFe2O4. The FTIR results showed the effect of heat treatment on Fe3O4@ZnFe2O4 core/shell nanoparticles. A simple method was used for the synthesis of Fe3O4@ZnFe2O4.

Franklinite was named by Pierre Berthier (1782–1861), a chemist and mineralogist at Ecole des Mines, Paris, France, in 1819. Berthier (1819) stated, “I propose to [name the new mineral] Franklinite...

Recycling of industrial waste has become a process of highly positive impact on the environment, industry and human health. The management of the electric arc furnace dust (EAFD) is a necessary and interesting task due to the possible recovery of its elevated metallic content (Zn, Pb, Cu, etc.). This reduces the environmental pollution generated by the leachability of its heavy metals and produces new revenues for the steel industries. In this work, a hydrometallurgical route was studied to extract the zinc present in EAFD. The research carried out using two carboxylic acids: sodium citrate and oxalic acid at moderate concentrations (≤ 0.5 M). The effect of pH, molar concentration and stirring speed was analyzed. Under pressure and ambient temperature, after 3 h of leaching, the results showed that both agents can leach zinc from waste, reaching metal extractions of approximately 50%. The more stable franklinite (ZnFe2O4) and hematite (Fe2O3) phases were not decomposed under these mild conditions. Citrate was especially promising due to its selectivity for zinc.

The effects of basicity and Al2O3 content on the chemistry of phases in iron ore sinter containing ZnO were investigated by Rietveld analysis of the X-ray diffraction (XRD) patterns. Bulk composition analysis was carried out using inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and wet-chemical analysis. The composition of each phase was investigated using a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDX). It was found that ZnO exists in the franklinite and the silicoferrite of calcium and aluminum (SFCA) phases. With increasing ZnO content, the phase fraction of the franklinite increased, while the fraction of SFCA slightly increased. When ZnO content was fixed at 1 wt pct and basicity increased, the fraction of franklinite decreased and that of SFCA increased. Here, the solubility of ZnO in the SFCA increased. As the Al2O3 content increased, the fraction of franklinite decreased and that of SFCA increased, while ZnO content in the SFCA did not change significantly.

Large industrial productions generate large amounts of waste, and researchers are investigating alternatives to reuse them. For instance, these wastes can used to produce ceramic pigments in the ceramic tile industry. Electric-arc furnace dust (EAFD) is waste generated in the steelmaking process through the volatilization of metals from scrap and exhibits great potential for its use as a raw material in the production of ceramic pigments. The aim of this study is to produce glazes containing EAFD for ceramic tiles. The EAFD was characterized via laser diffraction, wavelength-dispersive X-ray fluorescence (WDXRF) spectroscopy, X-ray diffraction (XRD), thermogravimetric (TG), and differential thermogravimetric (DTG) analyses. Two glaze types (BGS and CBT) were produced with 2, 4, 6, and 8 wt.% EAFD and characterized via the Commission Internationale de I´Éclairage (CIE) L*a*b* values, abrasion resistance, and XRD. According to the particle size distribution analysis, the average particle size of the EAFD is 0.770 μm. Further, the chemical WDXRF analysis revealed that 44.60% of the EAFD is iron oxide and 26.24% is zinc oxide. According to the structural XRD analysis, the major crystalline phases of the EAFD are zincite, franklinite, magnetite, and other phases with spinel structures. The EAFD exhibits stability close to the firing temperature of the ceramic tiles (1130 °C). In addition, the ceramic tiles covered with both glazes became darker with increasing EAFD amount. These samples obtained a PEI 3 rating based on the abrasion analysis. Keywords: Glaze, Ceramic tiles, Electric-arc furnace dust (EAFD)

Nowadays, Nexa Resources (ex-Votorantim Metais) operates two zinc mines in Brazil, represented by the Vazante unit in Vazante - MG and the Morro Agudo unit in Paracatu - MG. The present study was carried out at the Vazante unit, where zinc concentrate is produced from a silicate ore called Willemite (Zn2SiO4) through froth flotation processes. The two main objectives of the study were the determination of the maximum zinc recovery that could be obtained in flotation bench tests with specific controlled conditions and the mineral characterization of the tailings generated, using a SEM/EDS (scanning electron microscope with energy dispersive x-ray spectroscopy) with MLA (mineral liberation analyzer). The flotation results showed a maximum recovery of 91.91 % with 1.68 % of zinc in the tailings after an eleven-minute flotation. Considering the mean results of all the tests, the maximum zinc recovery obtained was 91.07 % with 1.75 % zinc grade in the tailings. Mineral characterization analysis showed that zinc minerals besides Willemite, such as Gahnite and Franklinite are present in the zinc tailings. In addition, the analysis demonstrated that the Willemite present in the tailings is very fine (80 % < 0.015 mm) and well liberated. With no liberation problems, it was concluded that the main reason responsible for preventing zinc recovery to increase even more along the flotation tests was the presence of the extremely fine Willemite minerals. The test results showed that, to increase zinc recovery, two main processes needed to be considered. The grinding process, that will need to be improved and carefully revised to reduce Willemite fine grain size generation; and the flotation process, regarding bubble formation, reagent addition, resident time and a redesign of flotation machines, aiming to increase the recovery of extremely fine Willemite ore particles.

This study aims at detailed characteristics and comparison between dusts from various iron and non-ferrous metal production processes in order to identify individual mineral phases, chemical composition, and their influence on the values of magnetic susceptibility. Various analytical methods used include inductively coupled plasma optical emission spectroscopy, X-ray diffraction, scanning electron microscopy, and Mössbauer spectroscopy integrated with magnetic susceptibility measurements and thermomagnetic analysis. Metallurgical wastes that have arisen at different production stages of iron and non-ferrous steel are subjected to investigation. The analyzed dust samples from the iron and non-ferrous metallurgy differ in terms of magnetic susceptibility as well as their mineral and chemical composition. The research confirmed the presence of many very different mineral phases. In particular, interesting phases have been observed in non-ferrous dust, for example challacolloite, which was found for the first time in the dusts of non-ferrous metallurgy. Other characteristic minerals found in non-ferrous metallurgy dusts are zincite, anglesite, and lanarkite, while dusts of iron metallurgy contain mostly metallic iron and iron-bearing minerals (magnetite, hematite, franklinite, jacobsite, and wüstite), but also significant amounts of zincite and calcite.

Millions of tons of bottom ash (BA) is generated from incineration of industrial and municipal solid waste each year within EU. The magnitude of leaching of metals like Cu and Zn is critical for hazard and risk assessment of these ashes. Although speciation of metals is a key factor to understand and predict metal leaching, speciation of Cu and Zn in BA is not well known. In this study six metal separated and carbonized BA were investigated by a combination of X-ray absorption spectroscopy, X-ray diffraction, leaching/extraction tests, and geochemical modelling. Five of the BA were from grate boilers and one from a fluidized bed incinerator. The aims were to identify similarities in Cu and Zn speciation and to identify main species. The combination of several techniques was necessary to draw conclusions about speciation and displayed coherent results. A similar speciation of Cu and Zn was indicated in the five studied grate boiler ashes although the proportions between species may vary. Copper(II) oxide and Cu metal were the main Cu species in all BA. Zinc(II) oxide and willemite (Zn2SiO4) were identified in grate boiler ashes. The fluidized bed ash contained Zn-Si-minerals and possibly franklinite or gahnite, while the Zn(II) oxide content was low, if any. The results have implications for classification and risk assessment of MIBA. (C) 2020 The Authors. Published by Elsevier Ltd.

Coarse sludge (sample A) and fine sludge (sample B) from a Brazilian Linz–Donawitz—LD steelworks integrated plant was characterized. Chemical analysis determined high-level content of iron (51.54–77.53%) and lower grades of zinc (0.49–1.69%). XRD analysis permitted to observe various mineralogical phases, such as metallic iron, wustite, franklinite, magnetite, portlandite, periclase, calcite, calcium oxide, silicon, moissanite-2H, and srebrodolskite. Microscopic Optical and Scanning Electron Microscopic studies shown morphologies of these residues were made up of globular and skeletal aggregates of metallic iron intergrown with crystals of iron oxides, especially wustite and a significant presence of calcite and calcium oxide in spherical nodes having particle sizes between 0.12 and 0.15 mm. Scanning Electron Microscopy–Energy-Dispersive X-ray spectroscopy studies denoted significant content of Fe, O, and Ca in both samples. In addition, a thermogravimetric analysis by DTG–DSC–TG at 1000 °C exhibited a mass loss of 97.43% for sample A and 92.57% for sample B.

The mobility of Zn, Cd, Pb, Cu, and As was assessed in an atmospheric environment and soil system near a Zn smelter by performing sequential extraction as well as Pb isotopic and mineralogical analyses for fugitive and roof dusts and agricultural soils. Transmission electron microscopy observations with selected area electron diffraction patterns confirmed that micron-sized roof dusts originated from the Zn smelter. Both fugitive and roof dusts contained zincite, massicot, franklinite, anglesite, and willemite. The sequential extraction of the fugitive dust from the Zn smelter stacks showed that Zn, Cd, and Pb were predominantly bound to the exchangeable (FI), carbonate (FII), and reducible (FIII) fractions, whereas Cu and As were significantly associated with the residual (FV) fraction and had low mobility. The estimation of remobilized concentrations of Zn, Cd, and Pb bound to labile fractions (FI and FII) in the fugitive dust implied their severe environmental and human health risks. In contrast, the studied metal(loid)s in the roof dust had low mobility except for Pb, implying the insignificant risks of roof dusts, although anthropogenic dusts from the Zn smelter significantly impacted FV as well as the non-residual fractions based on the Pb isotopic compositions of geochemical fractions. Similarly, the mobility and bioavailability of the studied metal(loid)s were low in agricultural soils, except for Cd, suggesting a low adverse effect on crops cultivated in the soil. The decrease in labile Cd fractions with depth indicated that the agricultural soil did not retain anthropogenic Cd in the soil subsurface. The mineralogical investigation combined with sequential extraction revealed that the different mobility of Zn, Cd, and Pb between fugitive dusts, roof dusts and agricultural soils resulted from the different solubility of metal-bearing minerals, e.g., zincite, willemite, simonkolleite which were not detected in the residuals of the fugitive dust collected after FIII extraction.

Microwave (MW) assisted chloride leaching was studied to remove valuable and heavy metals from two zinc plant residues,i.e.goethite sludge and Zn-leach product. For both materials, NaCl leaching parameters, such as temperature, NaCl concentration, leaching time and addition of acid, were optimized. For goethite sludge, the best efficiencies for Cu (45–47 %), Pb (83–90 %), and Zn (47–58 %) extraction, with a minimal dissolution of matrix elements, were obtained at 200 °C, 300 g/L NaCl and L/S 10. At short leaching times (5 min) the maximal leachability of Cu and Zn was reached, while at longer leaching time (60 min) the Pb extraction increased to 90 ± 1%. Zn leaching was limited due to the presence of stable franklinite (ZnFe2O4). NaCl (280 g/L) leaching of Zn-leach product required the addition of 1 M HCl to improve metal leaching to Ag 52 ± 3 %, Bi 83 ± 1 %, Cd 82 ± 4 %, Sb 39 ± 1 %, Zn 71 ± 2 % at 200 °C, L/S 10 for 30 min. Consequently, matrix dissolution was enhanced. Metal associations in Zn-leach product were statistically investigated. The environmental impact of the MW leached materials was evaluated by a one stage leaching test, which showed a significant overall reduction in heavy metal leachability compared to untreated materials.

Previous studies have suggested that understanding soil metal speciation, rather than relying solely on total metal content, can improve the accuracy and utility of contaminated site risk assessments. Because soil properties and reaction time can alter metal speciation, speciation should influence metal bioaccessibility. For example, under gastrointestinal conditions, it is expected that metal species will differ in bioaccessibility depending on their stability in acidic pH environments. We studied the links between metal speciation and bioaccessibility. A combination of synchrotron-based X-ray diffraction and X-ray absorption near edge structure (XANES) was used to identify the zinc (Zn) speciation in spiked and smelter-affected soils. After conducting in vitro digestion tests on the soil samples, XANES and linear combination fitting were carried out on the residual pellets to identify the species of Zn that remained after digesting the soils in the simulated gastric and duodenal fluids. The metal species that were not present in the residual pellets were inferred to have been dissolved and, thus, more bioaccessible. Sphalerite (ZnS), ZnO, and outer-sphere Zn contributed more to Zn bioaccessibility than franklinite (ZnFe2 O4 ) and Zn incorporated into a hydroxy interlayer mineral (Zn-HIM). The bioaccessibility of Zn-aluminum layered double hydroxides (Zn-Al-LDH) was found to be inversely proportional to its residence time in soil. It was also observed that the relatively high pH of the duodenum favors metal reprecipitation and readsorption, leading to a reduction in bioaccessible metal concentration. These results imply that metal speciation mainly controls metal bioaccessibility. Environ Toxicol Chem 2019;38:448-459. © 2018 SETAC.

The sample used for this study was a sulfide flotation concentrate that came from PT Lumbung Mineral Sentosa.The phase changes that occur in the particles of zinc sulfide concentrate during roasting in a muffle furnace were investigated using light microscopy, X-ray diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS) while its chemical composition was analyzed using atomic absorption spectroscopy (AAS) and X-ray fluorescence (XRF) methods. Characterization also employed DTA-TGA instrument to provide data on the transformations that have occurred while the TGA data presents information about physical and chemical phenomena. Mineral composition of the sample included sphalerite, galena, chalcopyrite, and pyrite. Sphalerite was the most dominant one. Roasting sphalerite samples was intended to release the sulfur from its sulfide, Such a release was made easier for further treatment of the zinc such as a leaching process. Roasting temperature varied from 200 - 1,100 °C. Sphalerite starts to change when the temperature was raised to 650 °C performing the formation of zincite, franklinite, quartz and sphalerite as well. This composition did not change although the temperature increased to 1,100 °C. The Zn content within the original sample was 59.00% and then increased with the increasing of temperature but the improved in line with the increased temperature. The highest Zn was 78.98% achieved at 1,100 °C.

Zn, Fe modified SnO2 powders were prepared by sol-gel method using Tripropylamine as chelating agent and Polyvinylpyrrolidone K90 as dispersant and stabilizer. Two compositions were taken into account: Zn, Fe modified SnO2 – 20 mol% Zn, 10 mol% Fe and Zn, Fe modified SnO2 – 20 mol% Zn, 30 mol% Fe, denoted further as SZFe1and SZFe2 respectively. The properties and the influence of Fe amount on structure, morphology and surface chemistry, electrical and magnetic properties have been investigated. The X-ray diffraction analysis showed the formation of a polycrystalline mixture of cassiterite – SnO2, hematite – Fe2O3, franklinite – ZnFe2O4 and zincite – ZnO for the samples with different Fe content. The magnetization of SZFe2 sample was found to be composed of a ferromagnetic and a paramagnetic phase. The presence of Fe in the powders composition improved the electrical properties, demonstrating performant features in sensing characteristics (tested in CO gas concentrations varied from 50 to 1000 ppm). The magnetic investigations suggest their possible future applications as soft magnetic materials.

A new mineral species zincovelesite-6N6S with the simplified formula Zn3(Fe3+,Mn3+,Al,Ti)8O15(OH) was discovered in the orogenetic zone related to the “Mixed Series” metamorphic complex near the Nežilovo village, Jacupica Mountains, Pelagonia mountain range, Republic of Macedonia. In oxide Zn-Fe-Mn ore, zincovelesite-6N6S forms lenticular aggregates up to 2 × 2 × 0.5 mm consisting of thin near-coplanar platelets up to 70 × 70 × 1 µm3 and associated with franklinite, gahnite, hetaerolite, zincochromite, ferricoronadite, baryte, As-rich fluorapatite, dolomite, Zn-bearing talc, almeidaite, hydroxycalcioromeite, zircon, quartz, and scheelite. In silicate-baryte zones of the metasomatic rock, uniaxial intergrowths of zincovelesite-6N6S with nežilovite are observed. The new mineral is opaque, black, with brownish-black streak. The lustre is strong submetallic to metallic. The micro-indentation hardness is 1118 kg/mm2 which corresponds to Mohs’ hardness ca. 6½. Zincovelesite-6N6S is brittle, with uneven fracture. No cleavage or parting is observed. The density calculated from the empirical formula is 5.158 g/cm3. In reflected light zincovelesite-6N6S is light grey. The reflectance values [Rmax/Rmin, % (λ, nm)] are: 17.1/13.4 (470), 16.5/12.8 (546), 16.2/12.6 (589), 15.6/12.2 (650). The IR spectrum shows the presence of OH groups. According to the Mossbauer spectrum, all iron is trivalent. The Mn K-edge XANES spectroscopy shows that Mn is predominantly or completely trivalent. The average chemical composition is (wt%; electron microprobe, H2O determined by gas chromatography of ignition products): MgO 0.97, CuO 0.50, ZnO 30.80, Al2O3 8.17, Mn2O3 21.31, Fe2O3 29.44, TiO2 5.28, Sb2O5 3.74, H2O 1.1, total 101.31. The empirical formula based on 16 O atoms is H1.05Zn3.26Mg0.21Cu0.05Fe3+3.18Mn3+2.32Al1.38Ti0.57Sb0.20O16. Zincovelesite-6N6S is trigonal, probable space group P-3m1, a = 5.902(2) A, c = 55.86(1) A, V = 1684.8(9) A3, Z = 6. The strongest lines of the powder X-ray diffraction pattern [d, A (I, %) (hkl)] are: 2.952 (62) (110), 2.881 (61) (1.0.16), 2.515 (100) (204), 2.493 (88) (1.1.12), 2.451 (39) (1.0.20), 1.690 (19) (304, 2.1.16), 1.572 (19) (2.0.28), 1.475 (29) (221). Zincovelesite-6N6S is the first Fe3+-dominant member of the hogbomite supergroup and, thus, can be considered as a parent species of a new mineral group. The rootname velesite is given for the discovery locality near the city of Veles.

Blast furnace dust is a typical secondary resource produced in manufacturing iron. This substance contains many recyclable components, such as iron, lead, zinc, and carbon, which have not been properly utilized. Zinc is a dispersed component in blast furnace dust, but its volatility depends on its carrier minerals, such as hematite, coke, and silicate in descending order of zinc volatility. Volatilization is the necessary procedure of removing toxicity and recycling zinc from blast furnace dust. However, two critical limits exist: the amount of carbon in the residue and the amount of franklinite in the blast furnace dust. Zinc can be enclosed by the carbon grains according to kinetic analysis and energy dispersive spectrometer (EDS) tests. Therefore, the coke dosage should be controlled carefully to avoid carbon residue and increase the volatilization rate of zinc. Meanwhile, both franklinite and zincite are general zinc-bearing phases in the adopted dust, but neither can volatilize before being reduced to metallic form. Calculations show that the available reduction temperature of zincite is higher than that of franklinite. Nearly all the zinc in hematite and carbon is in the form of zincite and can be easily reduced in the heating process. However, the zinc in silicate mainly exists in the form of franklinite and is difficult to be reduced and volatilized, which explains the lower volatilization rate of zinc in silicate than in coke and hematite. In the last part of this investigation, the mineral phase and morphology of the volatiles obtained after fume reduction volatilization are tested for the first time to evaluate their potential application value. Only high-purity crystal zincite is found, which means that the volatiles can be used directly as high-grade zinc smelting materials without purification.

Electric arc furnace dust (EAFD) signifies a major source of recyclable zinc. Most of the zinc load in EAFD exists as zincite (ZnO) and franklinite (ZnFe2O4). The heterogenous mixture of EAFD renders it technologically challenging to extract the valuable zinc content in EAFD via commonly utilized hydrometallurgical and pyrometallurgical operations. Co-pyrolysis of EAFD with halogen-containing polymers (most notably polyvinyl chloride, PVC, and brominated flame retardants, BFRs) is currently deployed as a potent approach in the selective extraction of zinc from EAFD. A robust optimization of this process necessitates acquiring accurate and representative kinetic parameters of involved chemical reactions. Herein, we construct a microkinetic model that accounts the surface halogenation of zinc ions in franklinite into zinc halides (ZnCl2/ZnBr2). Governing reaction and activation energies for the dissociative adsorption of hydrogen halides and alkyl halides with a franklinite surface were computed with the DFT + U formalism. Products profiles from the constructed kinetic model are discussed in the context of literature available experimental measurements pertinent to transformation of zinc into zinc halides. The predicted temperature window for the synthesis of surface ZnCl2/ZnBr2 moieties coincides with analogous results inferred from pyrolysis experiments. Uptake of HCl and HBr by franklinite commences at 600 K and 500 K, respectively. The model satisfactorily illustrates chemical phenomena that dictate the mass loss curves in EAFD-PVC/BFRs formulations, most notably dehalogenation of halogenated alkanes, evaporation of zinc halides evaporation, and water evolution.

Mill scale is one of the most hazardous waste generated from the steelmaking industry. In 2014, around 16.4–32.8 million t of mill scale was generated all over the world. In this paper, we present recent results about the effect of the structure and microstructure of iron-rich glass-ceramics obtained from mill scale on their electrical behavior. Five iron-rich glass compositions were investigated. The crystalline phases of the crystallized (glass-ceramic) materials were identified by X-ray diffractometry, and phase content quantifications were performed by the Rietveld method. The crystallinity and porosity were also related to the electrical behavior of the glass-ceramics, which was determined by impedance spectroscopy, and the hardness, measured by the Vickers indentation method. Albite, andradite, anorthite, clinopyroxene, franklinite, nepheline, and spinel were shown to be the main crystalline phases present in the investigated compositions. The conductivity showed an increasing trend with the degree of crystallinity. This behavior was attributed to a decrease in porosity, an increase in the concentration of charge carriers in the glass phase (iron, Li+, and Na+), and an increase in the number of conduction paths through the glassy phase/crystalline phase interfaces. The relationship between hardness and crystallinity could not be verified due to the structural complexity of the glass-ceramics studied. However, a nearly linear relationship was found between the effect of porosity and hardness. The G2Z composition exhibited a hardness of 6.1 ± 0.5 GPa at 850 °C, which is a value in very good agreement with other iron-rich glass-ceramics studied.

Zinc (Zn) biofortification in rice improves human nutrition and contributes considerably to rice growth. However, available information on Zn extractability and quantitative knowledge of how Zn is bound in paddy soils from Southeast Asia, which is of immense importance for Zn nutrition in rice, is rather limited. Here, we identified and quantified Zn pools with different solubility in 150 paddy soil samples using single, selective, and eight-step sequential extractions. The pH conditions of the soils ranged from ultra-acidic to slightly alkaline. The amounts of Zn in the extractable pools indicated sufficient levels of potentially available Zn (median DTPA–extractable Zn = 1.5 mg kg −1 ) in most soils. Chemical speciation calculations based on CaCl 2 extraction and DTPA–extraction data suggested that Zn 2+ ion activities in these soils were relatively low and most likely controlled by release of incorporated Zn rather than by dissolution of known Zn mineral phases. Maximum Zn 2+ solubilities were furthermore related to the solubility of franklinite (ZnFe 2 O 4 ), which is controlled by the availability of Fe 3+ being limited by the pH-dependent solubility of Fe(III) (hydr–)oxides. Correspondingly, the sequential extraction results revealed that residual fraction (F8) and maximum acid-soluble fraction (F7) (contributed to 75% of the total Zn in soils) were the dominant Zn pools in the studied soils. The quantitative contribution of other fractions decreased in the following order: crystalline Fe oxides (F6) > Mn oxides (F3) ≈ organically bound (F4) > microcrystalline Fe oxides (F5) > mobile (F1) > mobilizable (F2). The acidic soils contained more Zn in the presumably highly mobile fraction (F1) than the neutral soils, whereas the neutral soils contained more mobilizable Zn fraction (F2) than the acidic soils. The correlation analysis suggested that the CaCl 2 – and DTPA–extractable Zn and Zn fractions were influenced by soil pH and soil constituents such as organic carbon, and amounts of crystalline and microcrystalline Fe/Mn oxides.

Utilization of dusts generated from steelmaking industries will avoid disposal of wastes, enhance the use of secondary raw material fines and save costs. Understanding the properties of dust is necessary before determining the suitable recycling method. The present paper describes the chemical, morphological and mineralogical characterization of steelmaking dusts produced in steel plants in Finland. In this paper three different steelmaking dusts: ferrochrome converter (CRC) and electric arc furnace stainless steel (EAFSS) dusts from Outokumpu (Tornio, Finland), and electric arc furnace carbon steel (EAFCS) dust from Ovako (Imatra, Finland) were characterized. The characterization study showed that, the dusts from carbon steelmaking (EAFCS) are rich in zinc, while the dusts from stainless steelmaking (CRC) and (EAFSS) are relatively low in zinc, but richer in chromium. The zinc contents in CRC, EAFSS and EAFCS dusts are 10.83, 19.84 and 35.76 wt%, respectively, while the chromium contents are 20.88, 3.19 and 0.47 wt%, respectively. In the dust from CRC, zinc is found as zinc oxide (zincite, ZnO), while in the dusts from EAFSS & EAFCS zinc is found mostly as zinc ferrite (franklinite, ZnFe2O4). Scanning electron microscopy (SEM) investigations indicated that CRC dust is dominated by non-spherical form and composed mainly of aggregates of irregular particles of chromite, in addition to zincite sphere. EAFSS dust particles are characterized by encapsulation phenomenon, franklinite particles enclosed inside calcium-iron-silicate glass sphere. Manganese (Mn) concentrations show positive correlation with Zn, which suggests the occurrence of Mn mainly with franklinite phase. EAFCS dust is dominated by spherical form, and zinc found as franklinite and zincite. In the large particles > 3 μm of EAFCS dust, franklinite enclosed inside glass sphere, while in finer particles The investigations indicate that steelmaking dusts from CRC, EAFSS, and EAFCS show significant difference in concentration and mode of occurrence of zinc in the dusts, which will influence the determination of suitable processing methods.

This chapter provides the survey scans and high resolution scans of the minerals belonging to the chemical class of the oxides and hydroxides together with tables of the peak positions and atomic ratios. Minerals covered in this chapter are: cuprite, periclase, corundum, hematite, perovskite, ilmenite, rutile, pyrolusite, cassiterite, anatase, brookite, thorianite, gahnite, magnetite, franklinite, chromite, minium, chrysoberyl. tantalite/columbite-(Fe,Mg,Mn), goethite, bohmite, manganite, brucite, gibbsite, bayerite, and romanechite.

Extended milling/mechanical activation properties of zinc plant residue was investigated using two different milling systems, namely, high speed vibrating ball mill and ring mill, comparatively. The zinc plant residue was mixture of gypsum, anglesite, massicot, quartz, maghemite, and franklinite. Zinc plant residue was milled for 1-30 min in high speed vibrating ball mill and ring mill. The obtained samples were characterized using XRD, SEM, particle size distribution, and N-2-BET methods. According to results, it was found that the ring mill caused a further decrease in particle size. Particle size distribution and N-2-BET analyses showed that agglomeration of particles began after 15 min and 5 min milling time for HSBVM and ring mill, respectively.

The Vazante deposit, which is the world's largest zinc silicate deposit, occurs in brecciated dolomite and comprises mainly willemite with various proportions of hematite, Fe-carbonate, minor franklinite and magnetite. Exploration for this type of deposit is more challenging than zinc sulfide deposits, as they do not exhibit similar geophysical anomalies. To improve the application of geophysical surveys to the exploration of hypogene silicate zinc deposits, data from 475 samples were investigated from drill holes representative of the various types of ore and host rocks as well as barren zones of known geophysical anomalies in the Vazante District. Lithogeochemical and mineralogical (optical, SEM and MLA) data were integrated with physical rock properties (density, magnetic susceptibility and K U Th gamma-ray spectrometry) to assist in exploring for this type of deposit. The most distinct physical property of the ore is density, compared with the host rocks due to high proportion of denser minerals (hematite and willemite). However, barren hematite breccias also have high densities. The zinc ore and hematite breccias yielded higher magnetic susceptibilities than the surrounding host rocks, with the highest values associated with greater proportions of franklinite and magnetite. The density and magnetic susceptibility contrasts are a result of hydrothermal fluids interacting with and altering the carbonate host rocks. Zinc ore also yielded elevated U concentrations relative to the various host rocks, yielding higher gamma-ray spectrometric values. The results of this investigation indicate that an integration of magnetic, gravimetric and radiometric surveys would be required to identify zinc silicate ore zones.

Zn-doped YIG was prepared using the sol–gel method with TGA measurements showing the phase formation between 900 and 1000 °C. XRD analysis showed close to 1100 °C the formation of Franklinite phase, coexisting with the cubic YIG. Y3(Fe1–xZnx)5O12 samples with different Zn concentrations (x = 0, 0.01, 0.03, and 0.05) were prepared and analyzed for a magnetic study. A decrease in magnetic moment of the samples was confirmed on increasing the concentration of Zn ions. This decrease is due to the substitution of Fe ions by Zn. This also confirmed the results of XRD showing the linear increase in the lattice parameter. Fittings by Bloch's law shows results compared with those already reported in the literature. The exponent and constant for the Bloch law presented similar values to those reported for YIG doped with other ions. We obtained the parameter α ∼10−6 K−n with n close to 1.9 for all samples.

A new mineral ferricoronadite with the simplified formula Pb(Mn6 4+Fe2 3+)O16 was discovered in the orogenetic zone related to the “Mixed Series” metamorphic complex near the Nežilovo village, Pelagonian massif, Republic of Macedonia. Associated minerals are franklinite, gahnite, hetaerolite, romeite, almeidaite, Mn-analogue of plumboferrite, zincohogbomite analogue with Fe3+ > Al, zincochromite, Zn-bearing talc, Zn-bearing muscovite, baryte, quartz and zircon. Ferricoronadite is a late hydrothermal mineral forming veinlets up to 8 mm thick in granular aggregate predominantly composed by zinc-dominant spinels. The new mineral is opaque, black, with brownish black streak. The luster is strong submetallic to metallic. The micro-indentation hardness is 819 kg/mm2. Distinct cleavage is observed on (100). Ferricoronadite is brittle, with uneven fracture. The density calculated from the empirical formula is 5.538 g/cm3. In reflected light, ferricoronadite is light gray. The reflectance values [R max/R min, % (λ, nm)] are: 28.7/27.8 (470), 27.6/26.6 (546), 27.2/26.1 (589), 26.5/25.5 (650). The IR spectrum shows the absence of H2O and OH groups. According to the Mossbauer spectrum, all iron is trivalent. The Mn K-edge XANES spectroscopy shows that Mn is predominantly tetravalent, with subordinate Mn3+. The chemical composition is (wt%; electron microprobe, Mn apportioned between MnO2 and Mn2O3 based on the charge-balance requirement): BaO 5.16, PbO 24.50, ZnO 0.33, Al2O3 0.50, Mn2O3 9.90, Fe2O3 11.45, TiO2 4.19, MnO2 44.81, total 100.84. The empirical formula based on 8 cations Mn + Fe + Ti + Al + Zn pfu is Pb1.03Ba0.32(Mn 4.85 4+ Fe 1.35 3+ Mn 1.18 3+ Ti0.49Al0.09Zn0.04)Σ8.00O16. The crystal structure was determined using single-crystal X-ray diffraction data. The new mineral is tetragonal, space group I4/m, a = 9.9043(7), c = 2.8986(9) A, V = 284.34(9) A3, Z = 1. In ferricoronadite, double chains of edge-sharing (Mn, Fe, Ti)-centered octahedra are connected via common vertices to form a pseudo-framework with tunnels containing large cations Pb and Ba. The strongest lines of the powder X-ray diffraction pattern [d, A (I, %) (hkl)] are: 3.497 (33) (220), 3.128 (100) (−130, 130), 2.424 (27) (−121, 121), 2.214 (23) (240, −240), 2.178 (17) (031), 1.850 (15) (141, −141), 1.651 (16) (060), 1.554 (18) (−251, 251). Ferricoronadite is named as an analogue of coronadite Pb(Mn6 4+Mn2 3+)O16 with the major charge-compensating octahedral cation Fe3+ instead of Mn3+.

The nanocomposites of Franklinite (Fe2O4Zn) doped Zincte (ZnO) were synthesized through wet chemical (co-precipitation) technique followed by heat treatment. Metal chlorides and metal oxides are used as precursors for the formation of composites. The asprepared sample composites were subjected to sintering for two hours at the temperature of 300 °C. The detail spectral study and the effect of concentration of precursor salt on the structural parameters were done by using XRD and Rietveld refinement method. The occurrence of two crystalline phases (Fe2O4Zn and ZnO) was estimated from XRD data through Rietveld refinement. It was observed that the Fe2O4Zn have a cubic structure with space group Fd-3m (227), whereas ZnO has hexagonal structure with space group P 63 mc (186). The Wyckoff positions and rietveld refinement parameters like goodness factor, Bragg R factor, Rp value, Rexp were calculated. Effect of varying concentration of precursor on development of complete ferrite phase of structure was discussed.

The current study investigates a novel redox technology based on synthetic franklinite-like zinc-ferrite nanomaterial with magnetic properties and redox nature for potential use in water treatment. Physicochemical characterization revealed the nanoscale size and AB(2)O(4) spinel configuration of the zinc-ferrite nanomaterial. The redox activity of nanoparticles was tested for degradation of diclofenac (DCF) pharmaceutical in water, without any added external oxidants and under dark experimental conditions. Results revealed ~90% degradation in DCF (10 μM) within 2 min of reaction using 0.17 g/L Zn(1.0)Fe(2.0)O(4). Degradation of DCF was due to chemical reduction by surface electrons on zinc-ferrite and oxidation by oxygen-based radicals. Three byproducts from reduction route and eight from oxidation pathways were identified in the reaction system. Reaction pathways were suggested based on the identified byproducts. Results demonstrated the magnetic zinc-ferrite is a standalone technology that has a great promise for rapid degradation of organic contaminants, such as DCF in water.

A novelty process based on acid leaching basic oxygen furnace sludge by means of medium of 2,5M H2SO4 and 1M HCl was proposed. The new medium used in the study leaches franklinite ZnFe2O4 present in the tested sludge, which is hardly soluble in weak sulphuric acid solutions and well soluble in HCl solutions. This allows for 100% zinc extraction from the basic oxygen furnace sludge. The component of the leaching medium in the form of a sulphuric acid solution transforms the calcium compounds contained in the basic oxygen furnace sludge into insoluble calcium sulphate. The study examined the effect of solid to liquid ratio S/L (g/mL), temperature, time and rotational speed of stirrer on zinc and iron extraction from the sludge. Optimal leaching conditions were: t = 120 min, T = 60 °C, n = 500 min−1, S/L: 0.2. The leached solid filtration product obtained after leaching, dried and magnetically processed is separated into pure iron-bearing concentrate, which contains 77% Fe3O4 and 23% Fe2O3 and calcium sulphate waste. Their composition is confirmed by the X-ray diffraction analysis. The use of ethyl alcohol to precipitate sulphate iron compounds is a new alternative to recover and reuse the precipitant. The pure iron sulphate compounds with different hydration are obtained, which is confirmed by the X-ray diffraction analysis. The utilitarian aim of the study was to specify technological guidelines of the presented process and its material balance. Acid leaching of basic oxygen furnace sludge helps solve the problem of lack of selectivity in acid leaching of zinc and iron. This suggests the possibility of comprehensive use of the obtained products.

SARI, Zeynel Abidin/0000-0001-5932-2141, WOS: 000490085200012, Zinc plant residue is a secondary metal source because it has precious metals such as zinc and lead. However, since this residue contains partial ferrite structure, there is no large-scale recovery in metallurgy industry. The aim of this study is to investigate the effect of mechanical activation of zinc plant residue in sodium hydroxide leaching. The results showed that mechanical activation obtained from high-energy mill had positive effect on the leaching of metals under condition of limited grinding time. Mechanical activation over 1 min caused the increase in particle size. It was also determined that specific surface area decreased due to onset of agglomeration of fine particles on the surface. Leaching efficiency of long-time milled residue was lower than short-time milled material's leaching. It was determined that lead dissolution from zinc plant residue was higher than zinc dissolution in all experiments due to the presence of zinc in ferrite structure as franklinite form. Furthermore, sodium hydroxide leaching of this residue could be considered as a selective leach, since no iron was present in the solution., Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [112M285]; TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK), This work was financially supported by the Scientific and Technological Research Council of Turkey (TUBITAK, No. 112M285). The authors would like to thank TUBITAK for financial support.

This paper is the first description of natural copper-rich oxide spinels. They were found in deposits of oxidizing-type fumaroles related to the Tolbachik volcano, Kamchatka, Russia. This mineralization is represented by nine species with the following maximum contents of CuO (wt.%, given in parentheses): a new mineral thermaerogenite, ideally CuAl2O4 (26.9), cuprospinel, ideally CuFe3+2O4 (28.6), gahnite (21.4), magnesioferrite (14.7), spinel (10.9), magnesiochromite (9.0), franklinite (7.9), chromite (5.9), and zincochromite (4.8). Cuprospinel, formerly known only as a phase of anthropogenic origin, turned out to be the Cu-richest natural spinel-type oxide [sample with the composition (Cu0.831Zn0.100Mg0.043Ni0.022)Σ0.996(Fe3+1.725Al0.219Mn3+0.048Ti0.008)Σ2.000O4 from Tolbachik]. Aluminum and Fe3+-dominant spinels (thermaerogenite, gahnite, spinel, cuprospinel, franklinite, and magnesioferrite) were deposited directly from hot gas as volcanic sublimates. The most probable temperature interval of their crystallization is 600⁻800 °C. They are associated with each other and with tenorite, hematite, orthoclase, fluorophlogopite, langbeinite, calciolangbeinite, aphthitalite, anhydrite, fluoborite, sylvite, halite, pseudobrookite, urusovite, johillerite, ericlaxmanite, tilasite, etc. Cu-bearing spinels are among the latest minerals of this assemblage: they occur in cavities and overgrow even alkaline sulfates. Cu-enriched varieties of chrome-spinels (magnesiochromite, chromite, and zincochromite) were likely formed in the course of the metasomatic replacement of a magmatic chrome-spinel in micro-xenoliths of ultrabasic rock under the influence of volcanic gases. The new mineral thermaerogenite, ideally CuAl2O4, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption. It forms octahedral crystals up to 0.02 mm typically combined in open-work clusters up to 1 mm across. Thermaerogenite is semitransparent to transparent, with a strong vitreous lustre. Its colour is brown, yellow-brown, red-brown, brown-yellow or brown-red. The mineral is brittle, with the conchoidal fracture, cleavage is none observed. D(calc.) is 4.87 g/cm3. The chemical composition of the holotype (wt.%, electron microprobe) is: CuO 25.01, ZnO 17.45, Al2O3 39.43, Cr2O3 0.27, Fe2O3 17.96, total 100.12 wt.%. The empirical formula calculated on the basis of 4 O apfu is: (Cu0.619Zn0.422)Σ1.041(Al1.523Fe3+0.443Cr0.007)Σ1.973O4. The mineral is cubic, Fd-3m, a = 8.093(9) Å, V = 530.1(10) Å3. Thermaerogenite forms a continuous isomorphous series with gahnite. The strongest lines of the powder X-ray diffraction pattern of thermaerogenite [d, Å (I, %) (hkl)] are: 2.873 (65) (220), 2.451 (100) (311), 2.033 (10) (400), 1.660 (16) (422), 1.565 (28) (511) and 1.438 (30) (440).

Acid mine drainage (AMD) due to the oxidation of sulphide bearing waste rock (WR) is a common environmental problem associated with coal extraction. Therefore, WRs from the Lakhra coal field in Pakistan, were studied to i) perform a mineralogical and chemical characterisation, ii) determine the AMD generating potential and iii) estimate the leachability of elements. The chemical and mineralogical composition was studied using ICP, XRF, XRD and SEM. Acid base accounting and weathering cell test determined the acid producing potential of WRs. Besides organic material, the WRs were composed of quartz, pyrite, kaolinite, hematite and gypsum with varying amounts of calcite, lime, malladerite, spangolite, franklinite and birnessite. The major elements Si, Al, Ca and Fe were in the range (wt.%) of 8–12, 6–9, 0.3–3 and 1–10, respectively, with high S concentrations (19.4–113.3 g/kg). Trace elements were in the range (mg/kg) As (0.3–8), Cd (0.2–0.4), Co (15–75), Cr (67–111), Cu (25–101), Hg (0.1–0.2), Ni (50–107), Pb (8–20) and Zn (75–135). The AMD potential of WRs ranged from − 70 to − 492 kg CaCO3/tonne. During the test period of 192 days, the pH of leachates from very acidic WRs was maintained from 1 to 2.5, whereas, the less acidic WRs produced leachates of mildly acidic (2.7) to neutral (7.3) pH. The leachates from very acidic WRs ranged in the element concentrations of Fe, SO42 − and Al from mg/L to g/L and As, B, Co, Cu, Mn, Ni and Zn from μg/L to mg/L. However, the leachates from less acidic WRs contained all major elements in mg/L and trace elements in μg/L concentrations except for B and Mn that ranged from μg/L to mg/L. The results show that the studied WRs have mild to strong acid producing potential and have the capacity to deteriorate natural water quality significantly. Therefore, necessary preventive or/and acid neutralising measures are strongly suggested.

Solid waste generation is one of the main problems in the steelmaking process. One of the most problematic waste products is the electric arc furnace dust, which is a by-product rich in iron and zinc and is present as zincite (zinc oxide) or franklinite (zinc ferrite). This work focuses on the reduction kinetics of synthetic zinc ferrite by gases containing hydrogen and carbon monoxide. This process was examined via forced stepwise isothermal analysis. The test was conducted at temperatures ranging from 500 to 950 °C. Reduction of zinc was accomplished using a mixture of hydrogen and carbon monoxide in order to simulate reformed natural gas. The results indicated that reduction of zinc ferrite occurred in two stages (550–750 °C and 800–900 °C). The first stage was characterized by iron oxide reduction, where a mix control between nucleation and diffusion was determined. The apparent activation energy obtained was 71.5 kJ mol−1. The second stage was characterized by zinc oxide reduction, where the controlling mechanism was identified as a mixed control between diffusion and phase boundary reaction. The apparent activation energy was 135.5 kJ mol−1. The formation of a dense layer of metallic iron around the unreacted core may have caused the apparent activation energy to increase.

This work covers initially a general thermodynamics assessment regarding the zinc ferrite (ZnFe2O4) behavior toward direct and reducing chlorination. Then, the use of alternative chlorination agents were also theoretically appreciated, before a set of experiments has been carried out with industrial residue (electric arc furnace dust). Besides identifying zinc ferrite (95.4 pct), the XRD analysis indicated the presence of ZnO (4.6 pct). Therefore, the main objective of the present work is related to a theoretical (thermodynamics) and experimental (kinetics) evaluation of the mentioned residue chemical behavior as submitted to chlorination methods. Several characterization methods were used, such as X-ray diffraction, scanning electron microscopy, X-ray fluorescence, mass spectroscopy (ICP-MS), and energy-dispersive X-ray spectroscopy (EDS). It was observed that zinc was present, mostly, in the form of zinc ferrite (franklinite). The thermodynamics study revealed that Zn has a more susceptible behavior regarding the oxides conversion into chlorides. However, this tendency is not necessarily associated with a selective reaction, as showed for the chlorination in the presence of carbon, as both iron and zinc chlorides formation is feasible. The experimental results have indicated that some reaction systems can be further studied in order to identify operational conditions that enable selective formations. So, it was observed that for the calcium chloride reaction conducted at 1273 K (1000 °C) for 30 minutes, the iron content in the residue slightly increases (with 15 pct removal), whereas the zinc content decreases from 20 to 12 pct (53 pct removal), suggesting complementary studies where this possible selectivity could be even more determinant. Such results have also indicated that the direct action of chlorine at 1073 K (800 °C) allowed complete removal of zinc, followed by conversion in the order of 40 pct in iron. Therefore, a complementary investigation over these alternatives is identified as a promising option in the field of electric arc furnace dust treatment, particularly when the Zn content is very low.

Electric arc furnace dust (EAFD) is a toxic waste which is mainly rich in iron oxide, zinc, and lead. Hydrometallurgical extraction of zinc from Jordanian EAFD in alkaline medium was investigated; NaOH, NaHCO3, and Na2CO3 were used as leaching agents. The pH values for the prepared solutions were 8.3, 8.2, and 12.55 for NaHCO3, Na2CO3, and NaOH, respectively. The effect of NaOH concentration (1, 3, 5, 7, and 9 M), contact time (5 min to 3 h), temperature (20, 40, and 60), and solid-to-liquid ratio (SLR; 20, 40, 80, and 120 mg/ml) on the leachability of zinc from EAFD were tested. The initial EAFD and the resulting leach residues were characterized using X-ray diffraction (XRD) and X-ray fluorescence (XRF). EAFD contained 25.9% Zn, 18.0% Fe, and 3.2% Pb. A maximum zinc recovery of 92.9% was achieved using 6 M NaOH at 60 °C with solid loading of 20 g/L and 3 h leaching time. NaHCO3 and Na2CO3 were not efficient leaching agents for Zn extraction since the recoveries were only 2.6 and 4.5%, respectively. Zn and Pb were depleted in the residues with an E-factor of 0.5–0.6 and 0.1–0.25, respectively. Iron was enriched in the residues; the E-factor was around 2. The EAFD contained mainly zincite, franklinite, and magnetite. After 3 h leaching, only traces of zincite exist in the residues, while sylvite and halite were completely dissolved.