Minerals

The gradual replacement of Ca²⁺ with Cu²⁺ ions in brushite (CaHPO₄·2H₂O) has been extensively studied and discussed. The approach adopted in this work has not been systematically explored in previous studies. This novel approach may prove beneficial for the production of Ca_1−xCu_xHPO₄·nH₂O materials with desired properties suitable for medical applications. Solutions of sodium dihydrogen orthophosphate dihydrate, NaH₂PO₄·2H₂O, calcium nitrate tetrahydrate, Ca(NO₃)₂·4H₂O, copper nitrate trihydrate, Cu(NO₃)₂·3H₂O, ammonium hydroxide solution, and diluted HCl were used for the preparation of these materials. At low Cu/Ca molar ratios (up to 0.25) in the starting solution, biphasic phosphate minerals were formed: brushite and sampleite. When the Cu/Ca molar ratio increases gradually from 0.67 to 1.5, sampleite-like mineral precipitates. Powdered XRD (X-ray diffraction), thermogravimetric (TG) analysis, and SEM (scanning electron microscopy) techniques were employed for the study of the microstructure of the produced materials for different degrees of Ca replacement with Mg. It is found that the Cu/Ca ratio in the starting solution can be adjusted to obtain materials with tailored composition. Thus, a new method of sampleite-like synthesis as a rare mineral is introduced in this study. Both phosphate minerals brushite and sampleite-like minerals are attractive as precursors of bioceramics and biocements. The search for such products that may decrease the possibility of post prosthetic or implant infection can be crucial in preventing devastating post-surgical complications. Full article

The paper presents the characteristics of products annealing at the temperatures of 2400 and 3000 °C of unburned carbon from coal fly ash in terms of its possible use as a starting material in the graphitization process. An amorphous substance (organic substance) with an admixture of some minerals has been found in samples subjected to graphitization. However, the graphite phase is dominant in products subjected to graphitization. Studies have also shown a diverse grain morphology in individual samples. The presence of plate-shaped and tube-shaped grains was found. As the graphitization temperature of the starting material increases (2400 and 3000 °C), the specific surface area in the graphitization products decreases. The total pore volume in the samples after the graphitization process was significantly lower than the pore volume of active carbons produced from other unburned carbon. Average pore diameter is similar to the pore diameter in active carbons. The reflectance value of the matrix for the sample graphitized at 3000 °C is characteristic for graphite. Unburned carbon from Polish fly ash can be used as the starting material for graphitization. Full article

The construction of a repository for geological disposal of radioactive waste will include the use of cement-based materials. Following closure, groundwater will saturate the repository and the extensive use of cement will result in the development of a highly alkaline porewater, pH > 12.5; this fluid will migrate into and react with the host rock. The chemistry of the fluid will evolve over time, initially high [Na] and [K], evolving to a Ca-rich fluid, and finally returning to the groundwater composition. This evolving chemistry will affect the long-term performance of the repository, altering the physical and chemical properties, including radionuclide behaviour. Understanding these changes forms the basis for predicting the long-term evolution of the repository. This study focused on the determination of the nature and extent of the chemical reaction, as well as the formation and persistence of secondary mineral phases within a mudstone, comparing data from sequential flow experiments with the results of reactive transport modelling. The reaction of the mudstone with the cement leachates resulted in small changes in pH with the precipitation of calcium aluminium silicate hydrate (C-(A-)S-H) phases of varying compositions. As the system evolves, secondary C-(A-)S-H phases re-dissolve and are replaced by secondary carbonates. This general sequence was successfully simulated using reactive transport modelling. Full article

The ⁴⁰Ar/³⁹Ar method applied to K-feldspars and muscovite has been often used to construct continuous thermal history paths between ~150–600 °C, which are usually applied to structural and tectonic questions in many varied geological settings. However, other authors contest the use of ⁴⁰Ar/³⁹Ar thermochronology because they argue that the assumptions are rarely valid. Here we review and evaluate the key assumptions, which are that (i) ⁴⁰Ar is dominantly redistributed in K-feldspars and muscovite by thermally-driven volume diffusion, and (ii) laboratory experiments (high temperatures and short time scales) can accurately recover intrinsic diffusion parameters that apply to geological settings (lower temperatures over longer time scales). Studies do not entirely negate the application of diffusion theory to recover thermal histories, although they reveal the paramount importance of first accounting for fluid interaction and secondary reaction products via a detailed textural study of single crystals. Furthermore, an expanding database of experimental evidence shows that laboratory step-heating can induce structural and textural changes, and thus extreme caution must be made when extrapolating laboratory derived rate loss constants to the geological past. We conclude with a set of recommendations that include minimum sample characterisation prior to degassing, an assessment of mineralogical transformations during degassing and the use of in situ dating. Full article

A suite of coal samples near a diabase dike were collected to investigate the petrographic, mineralogical, and geochemical characteristics of thermally altered coal in Datong Coalfield, China. Proximate analysis, vitrinite reflectance measurement, and petrographic analysis were applied to identify and characterize the alteration halo; optical microscope observation, qualitative X-ray diffractometry, and SEM-EDS were applied to study the phases, occurrence, and composition of minerals; XRF, ICP-MS, and AFS were applied to determine concentrations of major and trace elements; and the occurrence modes of elements were studied by correlation and hierarchical cluster analysis as well as SEM-EDS. The results demonstrated that the 3.6 m dike has caused an alteration halo of approximately 2 m in diameter. In addition, the thermally altered coals were characterized by high vitrinite reflectance, low volatile matter, and the occurrence of thermally altered organic particles. Dolomite and ankerite in the thermally altered coal may be derived from hydrothermal fluids, while muscovite and tobelite may be transformed from a kaolinite precursor. The average concentration of Sr in the Tashan thermally altered coal reached 1714 μg/g, which is over 12 times that of the Chinese coal; the phosphate minerals and Sr-bearing kaolinite account for this significant enrichment. The cluster analysis classified elements with geochemical associations into four groups: group 1 and 2 were associated with aluminosilicates, clays, and carbonates and exhibited enrichment in the coal/rock contact zone, indicating that the dike may be the source of the elements; group 3 included P₂O₅, Sr, Ba, and Be, which fluctuate in coals, suggesting that their concentrations were influenced by multiple-factors; group 4 did not manifest obvious variations in coals, implying that the coal itself was the source. Full article

The Alhué deposit (Melipilla, Chile) is an example of a hydrothermal Au-Ag-Zn(-Pb) vein system hosted within the volcanic rocks of the Las Chilcas Formation. The dominant ore minerals observed are free electrum and native gold associated with silver sulfosalts, and with magnetite and base metal sulphides, including pyrite +/− sphalerite-galena-chalcopyrite. The alteration assemblage in the veins mainly consists of quartz epidote-chlorite-actinolite with lesser smectite, amphibole, and calcite-kaolinite-garnet. Mineralized veins also contain variable amounts of base metals, some of which (e.g., copper and iron) are considered harmful to the extraction of precious metals. Iron and especially copper minerals are known cyanide consumers; ore type classification schemes that do not consider the detrimental effects of such mineralogy or process elements can ultimately result in metal losses from ore feed restrictions, as well as spikes in cyanide consumption and higher operating costs. Mineralogical and geological variation can nonetheless be managed by applying alternating modes of operation as demonstrated in this paper; the decision to switch between modes is governed by current and forecasted stockpile levels feeding into the process. Simulations based on experiences at the Alhué deposit are provided that demonstrate the importance of standardized operational modes and their potential impact on cyanide consumption control. Full article

Nickel smelting slag contains valuable metals including nickel and copper. Failure to recycle these metals wastes resources, and disposal of nickel slag in stockpiles results in environmental pollution. Nickel slag recycling is important, and metals can be recovered from slag by flotation. However, considering the complex forms in which valuable metals occur in nickel slag, high yields are difficult to achieve by direct flotation. In this study, nickel slag was modified by reduction and sulfurization to render it more amenable to metal recovery through flotation. The mechanism was assessed based on thermodynamics and elements’ phase distributions. Thermodynamic analyses indicated the feasibility of nickel slag modification by reduction–sulfurization smelting. The results of chemical phase analysis show that the forms in which valuable metals occur in nickel slag can be modified by reduction–sulfurization, and the proportion of metals existing in sulfide and free metal states in nickel slag can be increased. Compared with the direct flotation of raw slag, the recovery of nickel and copper from top-blowing slag increased by 23.03% and 14.63%, respectively. The recoveries of nickel and copper from settling slag increased by 49.68% and 43.65%, respectively. Full article

The use of alkaline pressure oxidation to pretreat refractory gold ore often results in insufficient gold recovery (<60%) in downstream thiosulfate leaching. To improve gold recovery, flotation was considered for the separation of carbonaceous matter (C-matter). In this study, the effect of MIBC on C-matter flotation was investigated to understand the role of the frother in bubble and froth formation and on flotation kinetics. MIBC dosages between 30 and 150 g/t were used in combination with 500 g/t of kerosene as a collector. The results showed that the recovery and selectivity of C-matter were improved with increasing MIBC dosages. Improved selectivity at higher MIBC dosages was attributed to faster C-matter recovery as bubble size decreased to the critical coalescence concentration (CCC) and to changes to the foam structure. Analysis of flotation kinetics showed that the flotation rate increased as the MIBC dosage increased due to the decreasing bubble size and the reduced induction time caused by the interaction between the collector and the frother. The results of this study explain the role of MIBC in C-matter flotation and can be used as a design basis for scavenger-cleaner flotation testing. Overall, the results show the potential for flotation as a means to improve gold recovery in thiosulfate leaching through the removal of C-matter. Full article

In this investigation, a laboratory-scale study to extract copper (Cu) from its oxide ore (0.425–11.2 mm particle size) was conducted using varied sulfuric acid (H₂SO₄) concentrations (0.05–0.5 M) as a lixiviant. Through a physicochemical and mineralogical analysis of real field ore samples from the Almalyk mine heap site (Tashkent, Uzbekistan), malachite was identified as a Cu-bearing mineral. Extraction rates were analyzed according to the ore particle size and acid concentration. The Cu extraction with the smallest particle size (in 24 h) varied between 76.7% and 94.26% at varied H₂SO₄ concentrations (0.05–0.5 M). Almost half (50%) of Cu was extracted from the ore within 4 and 72 h of contact time for 0.425–2 mm and 5.6–11.2 mm particle sizes, respectively, using 0.15 M H₂SO₄. Weeklong leaching experiments with 0.5 M H₂SO₄ revealed a higher copper extraction rate (≥73%) from coarse ore particles (5.6–11.2 mm). Along with the copper extraction, iron (29.6 wt%), aluminum (70.2 wt%), magnesium (85.4 wt%), and calcium (44.4 wt%) were also leached out considerably through the dissolution of silicate and carbonate gangue minerals. In this study, an 80.0–94.26% copper extraction rate with reduced acid consumption (20%) proved to be a cost-effective approach. Full article

During the Cretaceous period of the northern Songliao Basin (northeast of China), a 100 m thick layer of fluvial-phase sandstone (Sifangtai Formation) with uranium potential was widely deposited, but its geochemical characteristics, paleoenvironment, and provenance remain unknown. This research proposes a new set of relevant geochemical data for sandstones to investigate their paleoenvironment, provenance and tectonic setting. The results revealed that: (1) The sandstone of the Sifangtai Formation was dominated by feldspar lithic sandstone. Geochemical signatures demonstrate that these sandstones have a high silicon content (SiO₂ = 68.30~83.60 wt%) and total alkali content, but are poor in magnesium and calcium. They are also enriched in Rb, Th, U, K and LREE, and depleted HFSE (e.g., Nb, Ta), with crustal magmatic source. (2) The paleoclimate discriminant indicated that the rocks of the Sifangtai Formation might that the climate of Sifangtai Formation is semi-arid, and the chemical weathering of the source rocks is weak under the semi-arid climate environment. (3) The combination of element Sr/Ba, 100 MgO/Al₂O₃ and the combination of v/v + Ni, V/Cr, Ni/Co, and Sr/Cu indicated that the paleo-water medium was deposited in an oxygen-rich freshwater environment when the Sifangtai Formation was deposited. (4) The discriminate diagrams showed that almost all the sandstones of the Sifangtai Formation fell in the range of the active continental margin, indicating that the source area of the sandstones of Sifangtai Formations is an active continental margin tectonic environment, and the source is a felsic rock developed in the Xiaoxing’an Ridge and Zhangguangcailing area. Full article

Amphibole peridotite samples from Åheim, Norway, were analyzed to understand the deformation mechanism and microstructural evolution of olivine and amphibole through the Scandian Orogeny and subsequent exhumation process. Three Åheim amphibole peridotite samples were selected for detailed microstructural analysis. The Åheim amphibole peridotites exhibit porphyroclastic texture, abundant subgrain boundaries in olivine, and the evidence of localized shear deformation in the tremolite-rich layer. Two different types of olivine lattice preferred orientations (LPOs) were observed: B- and A-type LPOs. Electron backscatter diffraction (EBSD) mapping and transmission electron microscopy (TEM) observations revealed that most subgrain boundaries in olivine consist of dislocations with a (001)[¹⁰⁰] slip system. The subgrain boundaries in olivine may have resulted from the deformation of olivine with moderate water content. In addition, TEM observations using a thickness-fringe method showed that the free dislocations of olivine with the (010)[¹⁰⁰] slip system were dominant in the peridotites. Our data suggest that the subgrain boundaries and free dislocations in olivine represent a product of later-stage deformation associated with the exhumation process. EBSD mapping of the tremolite-rich layer revealed intracrystalline plasticity in amphibole, which can be interpreted as the activation of the (100)[⁰⁰¹] slip system. Full article

Pilot sites are currently used to test the performance of bentonite barriers for sealing high-level radioactive waste repositories, but the degree of mineral stability under enhanced thermal conditions remains a topic of debate. This study focuses on the SKB ABM5 experiment, which ran for 5 years (2012 to 2017) and locally reached a maximum temperature of 250 °C. Five bentonites were investigated using XRD with Rietveld refinement, SEM-EDX and by measuring pH, CEC and EC. Samples extracted from bentonite blocks at 0.1, 1, 4 and 7 cm away from the heating pipe showed various stages of alteration related to the horizontal thermal gradient. Bentonites close to the contact with lower CEC values showed smectite alterations in the form of tetrahedral substitution of Si⁴⁺ by Al³⁺ and some octahedral metal substitutions, probably related to ferric/ferrous iron derived from corrosion of the heater during oxidative boiling, with pyrite dissolution and acidity occurring in some bentonite layers. This alteration was furthermore associated with higher amounts of hematite and minor calcite dissolution. However, as none of the bentonites showed any smectite loss and only displayed stronger alterations at the heater–bentonite contact, the sealants are considered to have remained largely intact. Full article

Ds-type inclusions during production are an important factor affecting the performance and quality of manufactured 10B21 steel. To minimize Ds-type inclusions in steel and improve the production qualification rate of steelmaking plants, a refining slag system optimization scheme was proposed based on the analysis of current inclusion evolution during the steelmaking process, and industrial tests were conducted to verify improvements resulting from application of the proposed scheme. The results showed that the composition of Ds inclusions in 10B21 steel are mainly CaO–Al₂O₃–MgO–CaS–TiN, which exists in the form of calcium–magnesium aluminate coated with titanium nitride and calcium sulfide. The main reason for the formation of Ds inclusions is the poor fluidity of the refining slag and its low capability to absorb inclusions. The poor coverage of the refining slag on the molten steel during refining can easily cause secondary oxidation of the molten steel. Thus, the formation and growth of Ds-type inclusions are aggravated after the calcium feeding line and soft blowing operation. Here, we propose to minimize Ds inclusions using our optimized refined slag system. The mass percentage of the optimized slag system is CaO: 55–60%, Al₂O₃: 20–35%, SiO₂: 3–7%, MgO: 4–8%, (MnO + FeO) < 1%, and the basicity is controlled within the range of 7–11. We observed that our optimized refining slag system has a significantly improved ability to remove inclusions, particularly Ds inclusions, which improves the qualification rate of 10B21 steel. Full article

Numerical modelling techniques such as the discrete element method are now well established and extensively used in many applications including solid earth geoscience, materials science, geotechnical engineering and rock mechanics. The potential for this technique in understanding comminution mechanisms has been identified as highly promising. This work utilizes the discrete element method as a numerical laboratory to conduct investigations relevant to comminution that would otherwise be costly or time-consuming to perform in the field or laboratory. A benchmark numerical model for impact breakage of rock specimens is first established and validated against results of controlled laboratory experiments. Thereafter, the model is utilized to systematically investigate the potential dependency of ore breakage properties upon the prevalence of pre-existing fractures, as well as the mineralogical composition of the ore. These numerical experiments serve to highlight the potential for quantitatively relating the mechanical response of ore to its textural and mineralogical characteristics. Tandem utilization of numerical and laboratory experimentation to formulate and test hypotheses is a promising avenue to illuminate such relationships. Full article

Wastes from old electronic devices represent a significant part of the electronic scrap generated in developing countries, being commonly sold by collectors as low-value material to recycling hubs abroad. Upgrading the quality of this waste type could drive the revenue of recyclers, and thus, boost the recycling market. On this basis, this study investigated the possibility of concentrating metals from old wasted printed circuit boards through a physical separation-based route. Preparation of samples comprised fragmentation, size classification, density, and magnetic separation steps, followed by chemical and macro composition analysis. Cu, Al, Fe, and Sn constituted the major metals encountered in the scraps, including some peak concentrations of Zn, Sb, Pb, Ba, and Mn. Four distinct concentrate products could be obtained after suitable processing: (a) a light fraction composed of plastics and resins; (b) an aluminum concentrate; (c) a magnetic material concentrate, containing mainly iron; (d) a final concentrate containing more than 50% in mass of copper and enriched with nonferrous metals. Preliminary evidence showed that further processes, like the separation of copper wires through drumming, can potentially improve the effectiveness of the proposed processing circuit and should guide future works. Full article

This study aimed to evaluate the inhibitory effect of a series of ammonium adipate solutions (AASs) by using the linear expansion test, thermogravimetric analysis (TGA), and particle size distribution analysis, and to examine the underlying inhibitory mechanism. A series of AASs was prepared from adipic acid and amines as small-molecule inhibitors of oil shale rock swelling. They were then evaluated by the bentonite linear expansion test. The best one, namely, AAS-8 (synthesized with adipic acid and tetraethylenepentamine in a ratio of acid group to amine group of 1:2), was evaluated in a water-based drilling fluid. The linear expansion test showed that the linear expansion rate of AAS-8 was the lowest (59.61%) when the concentration was 0.1%. The evaluation of the drilling fluid revealed that AAS-8 had a strong inhibitory effect on the swelling of hydrated bentonite particles in the water-based drilling fluid and was compatible with carboxymethyl cellulose (CMC) and modified starch. The inhibition mechanism of AAS-8 was investigated using TGA and particle size distribution analysis, which demonstrated that AAS-8 might enter the clay layer and bind the clay sheets together by electrostatic adsorption and hydrogen bonding. Full article

With the decrease in high-grade chalcopyrite resources, the copper extraction from low-grade chalcopyrite has attracted more and more attention. However, the kinetic rates of chalcopyrite leaching with traditional oxidants are usually very slow due to the formation of the passivation layer. In this study, a novel reagent of chlorinated oxidant, trichloroisocyanuric acid (TCCA), was used to leach chalcopyrite for the first time. The experimental results showed that when the initial oxidant concentration for TCCA was 0.054 mol·L⁻¹, the leaching temperature was kept at 55 °C, and the pH of the pulp was controlled at 1, the oxidation efficiency of Cu can reach above 90% in less than 30 min. Various analyses of chalcopyrite mineral ore and its oxidized residues, such as chemical composition analysis, X-ray diffraction analysis, scanning electron microscopy analysis and X-ray photoelectron spectroscopy, were conducted, respectively. No obvious passivation layer was found on the chalcopyrite surface, though the sulfur product can also be generated during the leaching. Reaction kinetic analysis results showed that the different influence of surface reaction and diffusion process on the dissolution of chalcopyrite is little due to the fast leaching speed. After calculation, the activation energy of the whole leaching reaction is 9.06 kJ·mol⁻¹, much lower than that in other reports. The mechanism was also proposed that TCCA was hydrolyzed in the solution to form hypochlorous acid, which is the strong oxidant, and cyanuric acid, which prevents the formation of a passivation layer. The processing in this study is expected to be applied as a novel method for atmospheric leaching of chalcopyrite. Full article

Cretaceous strata preserved in Wyoming contain numerous large bentonite deposits formed from the felsic ash of volcanic eruptions, mainly derived from Idaho batholith magmatism. These bentonites preserve a near-continuous 40 m.y. chronology of volcanism and their whole-rock and mineral chemistry has been used to document igneous processes and reconstruct the history of Idaho magmatism as emplacement migrated across the Laurentian margin. Using LA-ICP-MS, we analyzed the U-Pb ages and Hf isotopic compositions of nearly 700 zircon grains from 44 bentonite beds from the Bighorn Basin, Wyoming. Zircon populations contain magmatic autocrysts and antecrysts which can be linked to the main pulses of the Idaho batholith and xenocrysts ranging from approx. 250 Ma to 1.84 Ga from country rocks and basement source terranes. Initial εHf compositions of Phanerozoic zircons are diverse, with compositions ranging from −26 to nearly +12. Based on temporal trends in zircon ages and geochemistry, four distinct periods of plutonic emplacement are recognized during the Mid- to Late Cretaceous that follow plutonic emplacement across the Laurentian suture zone in western Idaho and into western Montana with the onset of Farallon slab shallowing. Our data demonstrate the utility of using zircons in preserved tephra to track the regional-scale evolution of convergent margins related to terrane accretion and the spatial migration of magmatism related to changes in subduction dynamics. Full article

The northwestern Erguna Block, where a wide range of volcanic rocks are present, provides one of the foremost locations to investigate Mesozoic Paleo-Pacific and Mongol-Okhotsk subduction. The identification and study of Late Jurassic mafic volcanic rocks in the Badaguan area of northwestern Erguna is of particular significance for the investigation of volcanic magma sources and their compositional evolution. Detailed petrological, geochemical, and zircon U-Pb dating suggests that the Late Jurassic mafic volcanic rocks formed at 157–161 Ma. Furthermore, the geochemical signatures of these mafic volcanic rocks indicate that they are calc-alkaline or transitional series with weak peraluminous characteristics. The rocks have a strong MgO, Al₂O₃, and total alkali content, and a SiO₂ content of 53.55–63.68 wt %; they are enriched in Rb, Th, U, K, and light rare-earth elements (LREE), and depleted in high-field-strength elements (HFSE), similar to igneous rocks in subduction zones. These characteristics indicate that the Late Jurassic mafic volcanic rocks in the Badaguan area may be derived from the partial melting of the lithospheric mantle as it was metasomatized by subduction-related fluid and the possible incorporation of some subducting sediments. Subsequently, the fractional crystallization of Fe and Ti oxides occurred during magmatic evolution. Combined with the regional geological data, it is inferred that the studied mafic volcanic rocks were formed by lithospheric extension after the closure of the Mongol-Okhotsk Ocean. Full article