Editor’s Choice Articles

The Río Tinto, located in the Iberian Pyrite Belt (SW Spain), constitutes an extreme case of pollution by acid mine drainage. Mining in the area dates back to the Copper Age, although large-scale mining of massive sulfide deposits did not start until the second half of the 19th century. Due to acidic mining discharges, the Río Tinto usually maintains a pH close to 2.5 and high concentrations of pollutants along its course. From a detailed sampling during the hydrological year 2017/18, it was observed that most pollutants followed a similar seasonal pattern, with maximum concentrations during autumn due to the washout of secondary soluble sulfate salts and minimum values during large flood events. Nevertheless, As and Pb showed different behavior, with delayed concentration peaks. The dissolved pollutant load throughout the monitored year reached 5000 tons of Fe, 2600 tons of Al, 680 tons of Zn, and so on. While most elements were transported almost exclusively in the dissolved phase, Fe, Pb, Cr, and, above all, As showed high values associated with particulate matter. River water quality data from 1969 to 2019 showed a sharp worsening in 2000, immediately after the mine closure. From 2001 on, an improvement was observed. Full article

Corundum is not uncommon on Earth but the gem varieties of ruby and sapphire are relatively rare. Gem corundum deposits are classified as primary and secondary deposits. Primary deposits contain corundum either in the rocks where it crystallized or as xenocrysts and xenoliths carried by magmas to the Earth’s surface. Classification systems for corundum deposits are based on different mineralogical and geological features. An up-to-date classification scheme for ruby deposits is described in the present paper. Ruby forms in mafic or felsic geological environments, or in metamorphosed carbonate platforms but it is always associated with rocks depleted in silica and enriched in alumina. Two major geological environments are favorable for the presence of ruby: (1) amphibolite to medium pressure granulite facies metamorphic belts and (2) alkaline basaltic volcanism in continental rifting environments. Primary ruby deposits formed from the Archean (2.71 Ga) in Greenland to the Pliocene (5 Ma) in Nepal. Secondary ruby deposits have formed at various times from the erosion of metamorphic belts (since the Precambrian) and alkali basalts (from the Cenozoic to the Quaternary). Primary ruby deposits are subdivided into two types based on their geological environment of formation: (Type I) magmatic-related and (Type II) metamorphic-related. Type I is characterized by two sub-types, specifically Type IA where xenocrysts or xenoliths of gem ruby of metamorphic (sometimes magmatic) origin are hosted by alkali basalts (Madagascar and others), and Type IB corresponding to xenocrysts of ruby in kimberlite (Democratic Republic of Congo). Type II also has two sub-types; metamorphic deposits sensu stricto (Type IIA) that formed in amphibolite to granulite facies environments, and metamorphic-metasomatic deposits (Type IIB) formed via high fluid–rock interaction and metasomatism. Secondary ruby deposits, i.e., placers are termed sedimentary-related (Type III). These placers are hosted in sedimentary rocks (soil, rudite, arenite, and silt) that formed via erosion, gravity effect, mechanical transport, and sedimentation along slopes or basins related to neotectonic motions and deformation. Full article

We present new structural, petrographic, geochemical and geochronological data for the late Paleozoic–early Mesozoic granites and associated igneous rocks of the Taimyr Peninsula. It is demonstrated that large volumes of granites were formed due to the oblique collision of the Kara microcontinent and the Siberian paleocontinent. Based on U-Th-Pb isotope data for zircons, we identify syncollisional (315–282 Ma) and postcollisional (264–248 Ma) varieties, which differ not only in age but also in petrochemical and geochemical features. It is also shown that as the postcollisional magmatism was coming to an end, Siberian plume magmatism manifested in the Kara orogen and was represented by basalts and dolerites of the trap formation (251–249 Ma), but also by differentiated and individual intrusions of monzonites, quartz monzonites and syenites (Early–Middle Triassic) with a mixed crustal-mantle source. We present a geodynamic model for the formation of the Kara orogen and discuss the relationship between collisional and trap magmatism. Full article

Panasqueira is a world-class W-Sn-Cu lode-type deposit located in Portugal. It consists of a dense swarm of subhorizontal quartz lodes criss-crossed by several ENE–WSW and N–S fault zones, bordering Late Variscan granite and hosted in Late Ediacaran—Early Cambrian metasediments. The relative abundance and compositional variation (assessed with EPMA) of the main silicates, oxides and phosphates forming the quartz lodes and their margins were examined, aiming to explore: (i) mineral and geochemical zonation at the mine scale; and (ii) some conclusions on the chemical nature of prevalent fluid inflows and T-conditions of mineral deposition. Quartz lodes nearby or far from the known greisen-granite cupola display significant differences, reflecting multiple fluid influxes of somewhat distinct composition related to various opening and closing events extending for several My, ranging from an early “oxide–silicate stage” (OSS) to a “main sulfide stage” (MSS), and further on to a post-ore carbonate stage (POCS); however, a rejuvenation event occurred after MSS. The onset of OSS was placed at ca. 299 ± 5 Ma and the rejuvenation event at ca. 292 Ma. The OSS was confined to ≈500 ≤ T ≤ 320 °C, following rutile and tourmaline growth under ≈640 ≤ T ≤ 540 °C (depending on aSiO₂). The rejuvenation event (≈440–450 °C) preceded a late chlorite growth (≈250–270 °C) and the progression towards POCS. Full article

Geochemical modeling of precipitation reactions in the complex matrix of acid mine drainage is fundamental to understanding natural attenuation, lime treatment, and treatment procedures that separate constituents for potential reuse or recycling. The three main dissolved constituents in acid mine drainage are iron, aluminum, and sulfate. During the neutralization of acid mine drainage (AMD) by mixing with clean tributaries or by titration with a base such as sodium hydroxide or slaked lime, Ca(OH)₂, iron precipitates at pH values of 2–3 if oxidized and aluminum precipitates at pH values of 4–5 and both processes buffer the pH during precipitation. Mixing processes were simulated using the ion-association model in the PHREEQC code. The results are sensitive to the solubility product constant (K_sp) used for the precipitating phases. A field example with data on discharge and water composition of AMD before and after mixing along with massive precipitation of an aluminum phase is simulated and shows that there is an optimal K_sp to give the best fit to the measured data. Best fit is defined when the predicted water composition after mixing and precipitation matches most closely the measured water chemistry. Slight adjustment to the proportion of stream discharges does not give a better fit. Full article

Sulfides extracted from porphyry-type deposits can contain a number of metals critical for the global energy transition, e.g., Co and precious metals such as Au and Re. These metals are currently determined on composite mineral samples, which commonly results in their dilution. Thus, it is possible that some metals of interest are overlooked during metallurgical processing and are subsequently lost to tailings. Here, an advanced geochemical characterization is implemented directly on metal-bearing sulfides, determining the grade of each targeted trace metal and recognizing its specific host mineral. Results show that pyrite is a prime host mineral for Co (up to 24,000 ppm) and commonly contains Au (up to 5 ppm), while molybdenite contains high grades of Re (up to 514 ppm) and Au (up to 31 ppm). Both minerals represent around 0.2% of the mineralized samples. The dataset is used to evaluate the possibility of extracting trace metals as by-products during Cu-sulfide processing, by the addition of unit operations to conventional plant designs. A remarkable advantage of the proposed workflows is that costs of mining, crushing, and grinding stages are accounted for in the copper production investments. The proposed geochemical characterization can be applied to other porphyry-type operations to improve the metallic benefits from a single deposit. Full article

We propose a 3D-shape preferred orientation (SPO) measurement method of rigid grains using synchrotron micro-computational tomography (μ-CT). The method includes oriented sampling, 3D μ-CT imaging, image filtering, ellipsoid fitting, and SPO measurement. After CT imaging, all processes are computerized, and the directions of thousands of rigid grains in 3D-space can be automatically measured. This method is optimized for estimating the orientation of the silt-sized rigid grains in fault gouge, which indicates P-shear direction in a fault system. This allows us to successfully deduce fault motion sense and quantify fault movement. Because this method requires a small amount of sample, it can be applied as an alternative to study fault systems, where the shear sense indicators are not distinct in the outcrop and the fault gouge is poorly developed. We applied the newly developed 3D-SPO method for a fault system in the Yangsan fault, one of the major faults in the southeastern Korean Peninsula, and observed the P-shear direction successfully. Full article

Approaches to reutilization of diamond clay tailings in northern environments are considered in the example of the Subarctic region of Russia. The monitoring studies are conducted at storage facilities of Severalmaz PJSC where ca. 14 million cubic meters of waste rock are produced annually after kimberlite mining and processing. The tailings of diamond ore dressing waste are situated in complex geological conditions of high-groundwater influx and harsh cold climate with low levels of solar radiation and the average annual temperature below freezing point. Furthermore, the adjoining protected forests with a significant diversity of biogeocenoses and salmon-spawning rivers are affected by the storage area. Reducing the impact of the tailings can be achieved through the reuse of the stored clay magnesia rocks obtained from saponite-containing suspension. The experiments reveal the most promising ways of their application as potential secondary mineral raw materials: cement clinker and ceramics manufacture, integration of alkaline clay into the reclamation of acidic peat bogs, and production of aqueous clay-based drilling fluid. Field and laboratory tests expose the advantages and prospects of each suggested treatment technique. Full article

Due to the special properties of the ammonium salts, ammonium acetate and ammonium citrate were used to explore the best leaching conditions of rare earth with compound ammonium carboxylate. This paper explored the influence of the molar ratio, ammonium concentration, experimental temperature, and pH of the compound leaching agents on the leaching efficiency of rare earth and aluminum, and it analyzed the leaching process based on the leaching kinetics, which provides a new method for leaching rare earth from the weathered crust elution-deposited rare earth ore. The results showed that under the conditions where the molar ratio of ammonium acetate and ammonium citrate was 7:3 and the ammonium concentration was 0.15 mol/L, the leaching efficiency of rare earth was the highest when the pH of leaching agent was 4.0 and the experimental temperature was 313 K. Meanwhile, when CH₃COONH₄ and (NH₄)₃Cit were used to leach rare earth ore, the leaching reaction kinetics equation of rare earth and aluminum were obtained. In the temperature range of 283–323 K, the apparent activation energy of rare earth was 14.89 kJ/mol and that of aluminum was 19.17 kJ/mol. The reaction order of rare earth was 0.98 and that of aluminum was 0.79. The results were in accordance with the shrinking core model and indicate that the concentration of the leaching agent had a greater influence on rare earth than aluminum. This process can reduce the use of ammonium salt, and it is of great significance to extract rare earth elements from weathered crust elution-deposited rare earth ore and improve the utilization rate of resources. Full article

Seismic anisotropy of S-wave, trench-parallel or trench-normal polarization direction of fast S-wave, has been observed in the fore-arc and back-arc regions of subduction zones. Lattice preferred orientation (LPO) of elastically anisotropic chlorite has been suggested as one of the major causes of seismic anisotropy in subduction zones. However, there are two different LPOs of chlorite reported based on the previous studies of natural chlorite peridotites, which can produce different expression of seismic anisotropy. The mechanism for causing the two different LPOs of chlorite is not known. Therefore, we conducted deformation experiments of chlorite peridotite under high pressure–temperature conditions (P = 0.5–2.5 GPa, T = 540–720 °C). We found that two different chlorite LPOs were developed depending on the magnitude of shear strain. The type-1 chlorite LPO is characterized by the [001] axes aligned subnormal to the shear plane, and the type-2 chlorite LPO is characterized by a girdle distribution of the [001] axes subnormal to the shear direction. The type-1 chlorite LPO developed under low shear strain (γ ≤ 3.1 ± 0.3), producing trench-parallel seismic anisotropy. The type-2 chlorite LPO developed under high shear strain (γ ≥ 5.1 ± 1.5), producing trench-normal seismic anisotropy. The anisotropy of S-wave velocity (AVs) of chlorite was very strong up to AVs = 48.7% so that anomalous seismic anisotropy in subduction zones can be influenced by the chlorite LPOs. Full article

Three batches of Mg₂SiO₄-ringwoodites (Mg-Rw) with different water contents (C_H2O = ~1019(238), 5500(229) and 16,307(1219) ppm) were synthesized by using conventional high-P experimental techniques. Thirteen thin sections with different thicknesses (~14–113 μm) were prepared from them and examined for water-related IR peaks using unpolarized infrared spectra at ambient P-T conditions, leading to the observation of 15 IR peaks at ~3682, 3407, 3348, 3278, 3100, 2849, 2660, 2556, 2448, 1352, 1347, 1307, 1282, 1194 and 1186 cm⁻¹. These IR peaks suggest multiple types of hydrogen defects in hydrous Mg-Rw. We have attributed the IR peaks at ~3680, 3650–3000 and 3000–2000 cm⁻¹, respectively, to the hydrogen defects [V_Si(OH)₄], [V_Mg(OH)₂Mg_SiSi_Mg] and [V_Mg(OH)₂]. Combining these IR features with the chemical characteristics of hydrous Rw, we have revealed that the hydrogen defects [V_Mg(OH)₂Mg_SiSi_Mg] are dominant in hydrous Rw at high P-T conditions, and the defects [V_Si(OH)₄] and [V_Mg(OH)₂] play negligible roles. Extensive IR measurements were performed on seven thin sections annealed for several times at T of 200–600 °C and quickly quenched to room T. They display many significant variations, including an absorption enhancement of the peak at ~3680 cm⁻¹, two new peaks occurring at ~3510 and 3461 cm⁻¹, remarkable intensifications of the peaks at ~3405 and 3345 cm⁻¹ and significant absorption reductions of the peaks at ~2500 cm⁻¹. These phenomena imply significant hydrogen migration among different crystallographic sites and rearrangement of the O-H dipoles in hydrous Mg-Rw at high T. From the IR spectra obtained for hydrous Rw both unannealed and annealed at high T, we further infer that substantial amounts of cation disorder should be present in hydrous Rw at the P-T conditions of the mantle transition zone, as required by the formation of the hydrogen defects [V_Mg(OH)₂Mg_SiSi_Mg]. The Mg-Si disorder may have very large effects on the physical and chemical properties of Rw, as exampled by its disproportional effects on the unit-cell volume and thermal expansivity. Full article

Gravity migration is a fast imaging technique based on the migration concept to obtain subsurface density distribution. For higher resolution of migration imaging results, we propose a 3D regularized focusing migration method that implements migration imaging of an entire gravity survey with a focusing stabilizer based on regularization theory. When determining the model parameters, the iterative direction is chosen as the conjugate migration direction, and the step size is selected on the basis of the Wolfe–Powell conditions. The model tests demonstrate that the proposed method can improve the resolution and precision of imaging results, especially for blocky structures. At the same time, the method has high computational efficiency, which allows rapid imaging for large-scale gravity data. It also has high stability in noisy conditions. The developed novel method is applied to interpret gravity data collected from the skarn-type iron deposits in Yucheng, Shandong province. Migration results show that the depth of the buried iron ore in this area is 750–1500 m, which is consistent with the drilling data. We also provide recommendations for further mineral exploration in the survey area. This method can be used to complete rapid global imaging of large mining areas and it provides important technical support for exploration of deep, concealed deposits. Full article

Acid mine drainage (AMD), characterized by a high concentration of heavy metals, poses a threat to the ecosystem and human health. Bioelectrochemical system (BES) is a promising technology for the simultaneous treatment of organic wastewater and recovery of metal ions from AMD. Different kinds of organic wastewater usually contain different predominant organic chemicals. However, the effect of different energy substrates on AMD treatment and microbial communities of BES remains largely unknown. Here, results showed that different energy substrates (such as glucose, acetate, ethanol, or lactate) affected the startup, maximum voltage output, power density, coulombic efficiency, and microbial communities of the microbial fuel cell (MFC). Compared with the maximum voltage output (55 mV) obtained by glucose-fed-MFC, much higher maximum voltage output (187 to 212 mV) was achieved by MFCs fed individually with other energy substrates. Acetate-fed-MFC showed the highest power density (195.07 mW/m²), followed by lactate (98.63 mW/m²), ethanol (52.02 mW/m²), and glucose (3.23 mW/m²). Microbial community analysis indicated that the microbial communities of anodic electroactive biofilms changed with different energy substrates. The unclassified_f_Enterobacteriaceae (87.48%) was predominant in glucose-fed-MFC, while Geobacter species only accounted for 0.63%. The genera of Methanobrevibacter (23.70%), Burkholderia-Paraburkholderia (23.47%), and Geobacter (11.90%) were the major genera enriched in the ethanol-fed-MFC. Geobacter was most predominant in MFC enriched by lactate (45.28%) or acetate (49.72%). Results showed that the abundance of exoelectrogens Geobacter species correlated to electricity-generation capacities of electroactive biofilms. Electroactive biofilms enriched with acetate, lactate, or ethanol effectively recovered all Cu²⁺ ion (349 mg/L) of simulated AMD in a cathodic chamber within 53 h by reduction as Cu⁰ on the cathode. However, only 34.65% of the total Cu²⁺ ion was removed in glucose-fed-MFC by precipitation with anions and cations rather than Cu⁰ on the cathode. Full article

This paper presents an integrated major and trace element data and crystal size distribution analysis for zoned clinopyroxene phenocrysts hosted in variolitic and massive picrobasalts of the Suisaari Formation, Karelian Craton, Eastern Fennoscandian Shield. Clinopyroxenes in variolitic and massive lavas occur as unzoned, reverse, and normally zoned crystal. Oscillatory-zoned clinopyroxenes are only observed in variolitic lavas. The obtained data were examined in order to evaluate the contribution of magmatic processes such as magma mixing, contamination and fractional crystallization to the formation of various zoning patterns of clinopyroxene phenocrysts. Clinopyroxene phenocrysts in both variolitic and massive lavas originate from similar primary melts from a single magmatic source. The obtained data on composition and texture of clinopyroxene phenocrysts together with the crystal size distribution (CSD) analysis suggest that crystallization of the massive lavas mainly involves fractionation in a closed magmatic system, whereas the crystallization of the variolitic lavas is determined by processes in an open magmatic system. The results provide novel information on the evolution of Paleoproterozoic magmatic systems in the Karelian Craton. Full article

Linear regression is often used as a diagnostic tool to understand the relative contributions of operational variables to some key performance indicator or response variable. However, owing to the nature of plant operations, predictor variables tend to be correlated, often highly so, and this can lead to significant complications in assessing the importance of these variables. Shapley regression is seen as the only axiomatic approach to deal with this problem but has almost exclusively been used with linear models to date. In this paper, the approach is extended to random forests, and the results are compared with some of the empirical variable importance measures widely used with these models, i.e., permutation and Gini variable importance measures. Four case studies are considered, of which two are based on simulated data and two on real world data from the mineral process industries. These case studies suggest that the random forest Shapley variable importance measure may be a more reliable indicator of the influence of predictor variables than the other measures that were considered. Moreover, the results obtained with the Gini variable importance measure was as reliable or better than that obtained with the permutation measure of the random forest. Full article

The detailed mineralogical, physical and chemical characterization of nine samples of imported cosmetic talc and of two samples of talc from currently non-productive Mexican ore deposits (Oaxaca and Puebla States) is presented. The imported cosmetic talc was classified into two groups, considering whether they are packed in the country of origin or in Mexico and considering their price. X-ray diffraction, infrared short wave, thermogravimetric analysis and scanning electron microscopy were used for mineralogical characterization. For the physical characterization, colorimetry and laser granulometry were used. The chemical composition (major, trace elements) was studied by ICP-MS. It was concluded that only the highest priced and imported in packaged form talcs meet the specific purity requirements for a talc of cosmetic type. The talcs that are packed in Mexico and the talc of the studied Mexican deposits present mineralogical and chemical impurities that make their use difficult in the manufacture of high-quality cosmetic talc. The low-price talc should not be sold as cosmetic talc, and the regulations in Mexico on this subject should be reviewed and updated. Full article

Nine samples of carbonate-free sodalite-group minerals, including those with abnormally high contents of polysulfide groups, fluoride anion and carbon dioxide molecules as well as synthetic fluoraluminate sodalite-type compound Na₈(Si₇Al₅O₂₄)(AlF₆)^3–·5H₂O, have been studied by means of electron microprobe analyses, infrared and Raman spectroscopy; the CO₂ content was determined using the selective sorption of gaseous ignition products. This article describes a semi-quantitative method for estimating the content of carbon dioxide molecules in these minerals, based on IR spectroscopy data. The data obtained demonstrate the existence of a sulfide sodalite-group mineral with the idealized formula Na₇(Si₆Al₆O₂₄)(S₃⁻)·H₂O, which differs significantly from the formula Na₆Ca₂(Si₆Al₆O₂₄)S^2–₂ accepted for lazurite. According to single-crystal X-ray structural analysis, in the F-rich sodalite-group mineral from the Eifel paleovolcanic region, Germany with the idealized formula Na₇(Si₆Al₆O₂₄)F⁻·nH₂O fluorine occurs as an isolated F⁻ anion, unlike synthetic F-rich sodalite-type compounds. Full article

The microstructure of amphibole peridotites from Åheim, Norway were analyzed to understand the evolution of the lattice-preferred orientation (LPO) of olivine throughout the Scandian Orogeny and its implication for the seismic anisotropy of the subduction zone. The Åheim peridotites had a porphyroclastic texture and some samples contained an abundant amount of hydrous minerals such as tremolite. Detailed microstructural analysis on the Åheim peridotites revealed multiple stages of deformation. The coarse grains showed an A-type LPO of olivine, which can be interpreted as the initial stage of deformation. The spinel-bearing samples showed a mixture of B-type and C-type LPOs of olivine, which is considered to represent the deformation under water-rich conditions. The recrystallized fine-grained olivine displays a B-type LPO, which can be interpreted as the final stage of deformation. Microstructures and water content of olivine indicate that the dominant deformation mechanism of olivine showing a B-type LPO is a dislocation creep under water-rich condition. The observation of the B-type LPO of olivine is important for an interpretation of trench-parallel seismic anisotropy in the mantle wedge. The calculated seismic anisotropy of the tremolite showed that tremolite can contribute to the trench-parallel seismic anisotropy in the mantle wedge. Full article

Nuclear resonant inelastic X-ray scattering (NRIXS) experiments have been applied to Earth materials, and the Debye speed is often related to the material’s seismic wave speeds. However, for anisotropic samples, the Debye speed extracted from NRIXS measurements is not equal to the Debye speed obtained using the material’s isotropic seismic wave speeds. The latter provides an upper bound for the Debye speed of the material. Consequently, the acoustic wave speeds estimated from the Debye speed extracted from NRIXS (Nuclear Resonant Inelastic X-ray Scattering) measurements are underestimated compared to the material’s true seismic wave speeds. To illustrate the differences, the effects of various assumptions used to estimate the Debye speed, as well as seismic wave speeds, are examined with iron alloys at Earth’s inner core conditions. For the case of pure iron, the variation of the crystal orientation relative to the incoming X-ray beam causes a $40\%$ variation in the measured Debye speed, and leads to 3% and 31% underestimation in the compressional and shear wave speeds, respectively. Based upon various iron alloys, the error in the inferred seismic shear wave speed strongly depends upon the strength of anisotropy that can be quantified. We can also derive Debye speeds based upon seismological observations such as the PREM (Preliminary Reference Earth Model) and inner core anisotropy model. We show that these seismically derived Debye speeds are upper bounds for Debye speeds obtained from NRIXS experiments and that interpretation of the Debye speeds from the NRIXS measurements in terms of seismic wave speeds should be done with utmost caution. Full article

Exploration under thick glacial sediment cover is an important facet of modern mineral exploration in Canada and northern Europe. Till heavy mineral concentrate (HMC) indicator mineral methods are well established in exploration for diamonds, gold, and base metals in glaciated terrain. Traditional methods rely on visual examination of >250 µm HMC material, however this study applies modern automated mineralogical methods (mineral liberation analysis (MLA)) to investigate the finer (<250 µm) fraction of till HMC. Automated mineralogy of finer material allows for rapid collection of precise compositional and morphological data from a large number (10,000–100,000) of heavy mineral grains in a single sample. The Izok Lake volcanogenic massive sulfide (VMS) deposit, one of the largest undeveloped Zn–Cu resources in North America, has a well-documented fan-shaped indicator mineral dispersal train and was used as a test site for this study. Axinite, a VMS indicator mineral difficult to identify optically in HMC, is identified in till samples up to 8 km down ice. Epidote and Fe-oxide minerals are identified, with concentrations peaking proximal to mineralization. Corundum and gahnite are intergrown in till samples immediately down ice of mineralization. Till samples also contain chalcopyrite and galena up to 8 km down ice of mineralization, an increase from 1.3 km for sulfide minerals in till previously reported for coarse HMC fractions. Some of these sulfide grains occur as inclusions within chemically and physically robust mineral grains and would not be identified visually in the coarse HMC visual counts. Best practices for epoxy mineral grain mounting and abundance reporting are presented along with the automated mineralogy of till samples down ice of the deposit. Full article

Xenophyllite, ideally Na₄Fe₇(PO₄)₆, is a rare meteoritic phosphate found in phosphide-phosphate assemblages confined to troilite nodules of the Augustinovka iron meteorite (medium octahedrite, IIIAB). The mineral occurs as tiny lamella up to 0.15 mm long cross-cutting millimeter-sized grains of sarcopside, Fe₃(PO₄)₂, associated with schreibersite, chromite and pentlandite. Xenophyllite is translucent, has a bluish-green to grey-green color and vitreous lustre. Moh’s hardness is 3.5–4. Cleavage is perfect on {001}. Measured density is 3.58(5) g/cm³. The mineral is biaxial (−), 2V 10–20°, with refractive indexes: α 1.675(2), β 1.681(2), γ 1.681 (2). Chemical composition of the holotype specimen (electron microprobe, wt.%) is: Na₂O 10.9, K₂O 0.4, MnO 5.8, FeO 42.1, Cr₂O₃ 0.8, P₂O₅ 40.7, total 100.7, corresponding to the empirical formula (Na_3.67K_0.09)_Σ3.76(Fe²⁺_6.12Mn²⁺_0.85Cr_0.11)_Σ7.08P_5.99O_24.00. Xenophyllite is triclinic, P1 or P-1, a 9.643(6), b 9.633(5), c 17.645(11) Å; α 88.26(5), β 88.16(5), γ 64.83(5)°, V 1482(2) ų, Z = 3. The toichiome C-centered subcell has the following dimensions: a 16.257(9), b 10.318(8), c 6.257(9) Å, β = 112.77(9)°, V 968(2) ų, Z = 2. Xenophyllite is structurally related to synthetic phosphate Kna₃Fe₇(PO₄)₆ having a channel-type structure, and galileiite, NaFe₄(PO₄)₃. The variations of chemical composition of xenophyllite ranging from Na₄Fe₇(PO₄)₆ to almost Na₂Fe₈(PO₄)₆ are accounted for by Na-ions mobility. The latter property makes xenophyllite a promising prototype for cathode materials used in sodium-ion batteries. Full article

This study investigates the time-dependent rheological behavior of cemented paste backfill (CPB) that contains alkali-activated slag (AAS) as a binder. Rheological measurements with the controlled shear strain method have been conducted on various AAS-CPB samples with different binder contents, silicate modulus (Ms: SiO₂/Na₂O molar ratio), fineness of slag and curing temperatures. The Bingham model afforded a good fit to all of the CPB mixtures. The results show that AAS-CPB samples with high binder content demonstrate a more rapid rate of gain in yield stress and plastic viscosity. AAS-CPB also shows better rheological behavior than CPB samples made up of ordinary Portland cement (OPC) at identical binder contents. It is found that increasing Ms yields lower yield stress and plastic viscosity and the rate of gain in these parameters. Increases in the fineness of slag has an adverse effect on rheological behavior of AAS-CPB. The rheological behavior of both OPC- and AAS-CPB samples is also strongly enhanced at higher temperatures. AAS-CPB samples are found to be more sensitive to the variation in curing temperatures than OPC-CPB samples with respect to the rate of gain in yield stress and plastic viscosity. As a result, the findings of this study will contribute to well understand the flow and transport features of fresh CPB mixtures under various conditions and their changes with time. Full article

Knowledge of the high-temperature properties of ternesite (Ca₅(SiO₄)₂SO₄) is becoming increasingly interesting for industry in different ways. On the one hand, the high-temperature product has recently been observed to have cementitious properties. Therefore, its formation and hydration characteristics have become an important field of research in the cement industry. On the other hand, it forms as sinter deposits in industrial kilns, where it can create serious problems during kiln operation. Here, we present two highlights of in situ Raman spectroscopic experiments that were designed to study the high-temperature stability of ternesite. First, the spectra of a natural ternesite crystal were recorded from 25 to 1230 °C, which revealed a phase transformation of ternesite to the high-temperature polymorph of dicalcium silicate (α’_L-Ca₂SiO₄), while the sulfur is degassed. With a heating rate of 10 °C/h, the transformation started at about 730 °C and was completed at 1120 °C. Using in situ hyperspectral Raman imaging with a micrometer-scale spatial resolution, we were able to monitor the solid-state reactions and, in particular, the formation properties of ternesite in the model system CaO-SiO₂-CaSO₄. In these multi-phase experiments, ternesite was found to be stable between 930 to 1020–1100 °C. Both ternesite and α’_L-Ca₂SiO₄ were found to co-exist at high temperatures. Furthermore, the results of the experiments indicate that whether or not ternesite or dicalcium silicate crystallizes during quenching to room temperature depends on the reaction progress and possibly on the gas fugacity and composition in the furnace. Full article

The Messinian microbialites of the Terminal Carbonate Complex (TCC) from the Neogene basins of southeastern Spain show both diversified morphologies and an excellent preservation of primary microbial microstructures. Their stratigraphic architecture, fabric (micro-, meso-, and macro-fabric), and mineralogical composition were investigated in eight localities from three sedimentary basins of southeastern Spain: The Sorbas and Bajo Segura basins and the Agua Amarga depression. Two recurrent microbialite associations were distinguished. Laterally linked low relief stromatolites predominated in Microbialite Association 1 (MA1), which probably formed in low energy lagoons or lakes with fluctuating normal marine to hypersaline water. The microfabrics of MA1 reflected the predominance of microbially induced/influenced precipitation of carbonates and locally (Ca)-Mg-Al silicates. Microbialite Association 2 (MA2) developed in high energy wave and tidal influenced foreshore to shoreface, in normal marine to hypersaline water. High-relief buildups surrounded by mobile sediment (e.g., ooids or pellets) dominated in this environment. MA2 microbialites showed a significant proportion of thrombolitic mesofabric. Grain-rich microfabrics indicated that trapping and binding played a significant role in their accretion, together with microbially induced/influenced carbonate precipitation. The stratigraphic distribution of MA1 and MA2 was strongly influenced by water level changes, the morphology and nature of the substratum, and exposure to waves. MA1 favorably developed in protected areas during third to fourth order early transgression and regression phases. MA2 mostly formed during the late transgressions and early regressions in high energy coastal areas, often corresponding to fossil coral reefs. Platform scale syn-sedimentary gypsum deformation and dissolution enhanced microbial carbonate production, microbialites being thicker and more extended in zones of maximum deformation/dissolution. Microbial microstructures (e.g., microbial peloids) and microfossils were preserved in the microbialites. Dolomite microspheres and filaments showed many morphological similarities with some of the cyanobacteria observed in modern open marine and hypersaline microbialites. Dolomite potentially replaced a metastable carbonate phase during early diagenesis, possibly in close relationship with extracellular polymeric substances (EPS) degradation. Double-layered microspheres locally showed an inner coating made of (Ca)-Mg-Al silicates and carbonates. This mineral coating could have formed around coccoid cyanobacteria and indicated an elevated pH in the upper part of the microbial mats and a potential dissolution of diatoms as a source of silica. Massive primary dolomite production in TCC microbialites may have resulted from enhanced sulfate reduction possibly linked to the dissolving gypsum that would have provided large amounts of sulfate-rich brines to microbial mats. Our results open new perspectives for the interpretation of ancient microbialites associated with major evaporite deposits, from microbe to carbonate platform scales. Full article

The viscosity of slag is a key factor affecting metallurgical efficiency and recycling, such as metal-slag reaction and separation, as well as slag wool processing. In order to comprehensively clarify the variation of the slag viscosity, various data mining methods have been employed to predict the viscosity of the slag. In this study, a more advanced dual-stage predictive modeling approach is proposed in order to accurately analyze and predict the viscosity of slag. Compared with the traditional single data mining approach, the proposed method performs better with a higher recall rate and low misclassification rate. The simulation results show that temperature, SiO₂, Al₂O₃, P₂O₅, and CaO have greater influences on the slag’s viscosity. The critical temperature for onset of the important influence of slag composition is 980 °C. Furthermore, it is found that SiO₂ and P₂O₅ have positive correlations with slag’s viscosity, while temperature, Al₂O₃, and CaO have negative correlations. A two-equation model of six-degree polynomial combined with Arrhenius formula is also established for the purpose of providing theoretical guidance for industrial application and reutilization of slag. Full article

The purpose of this work is to evaluate the long-term effects of radiation on the structure of naturally occurring apatite in the hope of assessing its potential for use as a solid nuclear waste form for actinide sequestration over geologically relevant timescales. When a crystal is exposed to radioactivity from unstable constituent atoms undergoing decay, the crystal’s structure may become damaged. Crystalline materials rendered partially or wholly amorphous in this way are deemed “partially metamict” or “metamict” respectively. Intimate proximity of a non-radioactive mineral to a radioactive one may also cause damage in the former, evident, for example, in pleochroic haloes surrounding zircon inclusions in micas. Radiation damage may be repaired through the process of annealing. Experimental evidence suggests that apatite may anneal during alpha particle bombardment (termed “self-annealing”), which, combined with a low solubility in aqueous fluids and propensity to incorporate actinide elements, makes this mineral a promising phase for nuclear waste storage. Apatite evaluated in this study occurs in a Grenville-aged crustal carbonatite at the Silver Crater Mine in direct contact with U-bearing pyrochlore (var. betafite)—a highly radioactive mineral. Stable isotope analyses of calcite from the carbonatite yield δ¹⁸O and δ¹³C consistent with other similar deposits in the Grenville Province. Although apatite and betafite imaged using cathodoluminescence (CL) show textures indicative of fracture-controlled alteration, Pb isotope analyses of betafite from the Silver Crater Mine reported in previous work are consistent with a model of long term Pb loss from diffusion, suggesting the alteration was not recent. Thus, it is interpreted that these minerals remained juxtaposed with no further metamorphic overprint for ≈1.0 Ga, and therefore provide an ideal opportunity to study the effects of natural, actinide-sourced radiation on the apatite structure over long timescales. Through broad and focused X-ray beam analyses and electron backscatter diffraction (EBSD) mapping, the pyrochlore is shown to be completely metamict—exhibiting no discernible diffraction associated with crystallinity. Meanwhile, apatite evaluated with these methods is confirmed to be highly crystalline with no detectable radiation damage. However, the depth of α-decay damage is not well-understood, with reported depths ranging from tens of microns to just a few nanometers. EBSD, a surface sensitive technique, was therefore used to evaluate the crystallinity of apatite surfaces which had been in direct contact with radioactive pyrochlore, and the entire volume of small apatite crystals whose cores may have received significant radiation doses. The EBSD results demonstrate that apatite remains crystalline, as derived from sharp and correctly-indexed Kikuchi patterns, even on surfaces in direct contact with a highly radioactive source for prolonged periods in natural systems. Full article

In Archean greenstone belts, magmatism is dominated by intrusive and volcanic rocks with tholeiitic affinities, as well as tonalite- and granodiorite-dominated large-volume batholiths, i.e., tonalite–trondhjemite–granodiorite (TTG) suites. These intrusions are associated with poorly documented mineralization (Cu-Au porphyries) that, in the Neoarchean Abitibi Subprovince (>2.79 to ~2.65 Ga), Superior Province, Canada, are associated with diorite bearing plutons, i.e., tonalite–trondhjemite–diorite (TTD) suites. The importance of TTG versus TTD suites in the evolution of greenstone belts and of their magmatic-hydrothermal systems and related mineralization is unconstrained. The aim of this study was to portray the chemistry and distribution of these suites in the Abitibi Subprovince. The study used data compiled by the geological surveys of Québec and Ontario to evaluate the chemistry of TTG and TTD suites and uncovered two coeval magmas that significantly differentiated (fractional crystallization mostly): 1) a heavy rare earth elements (HREE)-depleted tonalitic magma from high pressure melting of an hydrated basalt source; and 2) a hybrid HREE-undepleted magma that may be a mixture of mantle-derived (tholeiite) and tonalitic melts. The HREE-depleted rocks (mostly tonalite and granodiorite) display chemical characteristics of TTG suites (HREE, Ti, Nb, Ta, Y, and Sr depletion, lack of mafic unit, Na-rich), while the other rocks (tonalite and diorite) formed TTD suites. Tonalite-dominated magmatism, in the Abitibi Subprovince, comprises crustal melts as well as a significant proportion of mantle-derived magmas and this may be essential for Cu-Au magmatic-hydrothermal mineralizing systems. Full article

Barite (BaSO₄) and celestite (SrSO₄) are the end-members of a nearly ideal solid solution. Most of the exploitable deposits of celestite occur associated with evaporitic sediments which consist of gypsum (CaSO₄·2H₂O) or anhydrite (CaSO₄). Barite, despite having a broader geological distribution is rarely present in these deposits. In this work, we present an experimental study of the interaction between gypsum crystals and aqueous solutions that bear Sr or Ba. This interaction leads to the development of dissolution-crystallization reactions that result in the pseudomorphic replacement of the gypsum crystals by aggregates of celestite or barite, respectively. The monitoring of both replacement reactions shows that they take place at very different rates. Millimeter-sized gypsum crystals in contact with a 0.5 M SrCl₂ solution are completely replaced by celestite aggregates in less than 1 day. In contrast, only a thin barite rim replaces gypsum after seven days of interaction of the latter with a 0.5 M BaCl₂ solution. We interpret that this marked difference in the kinetics of the two replacement reactions relates the different orientational relationship that exists between the crystals of the two replacing phases and the gypsum substrate. This influence is further modulated by the specific crystal habit of each secondary phase. Thus, the formation of a thin oriented layer of platy barite crystals effectively armors the gypsum surface and prevents its interaction with the Ba-bearing solution, thereby strongly hindering the progress of the replacement reaction. In contrast, the random orientation of celestite crystals with respect to gypsum guarantees that a significant volume of porosity contained in the celestite layer is interconnected, facilitating the continuous communication between the gypsum surface and the fluid phase and guaranteeing the progress of the gypsum-by-celestite replacement. Full article

The southern part of the tropical Cayo Coco Island (Cuba) hosts a complex, highly evaporative and marine-fed lagoonal network. In the easternmost lagoon of this network, hypersaline conditions favour the development of complex sedimentary microbial ecosystems within the water column at the bottom water-sediment interface and on the shore. Some of these ecosystems are producing microbial mats and biofilms with variable mineralisation rates, depending on their location. Since the mineralisation of these microbial deposits is rare, the sedimentary record does not provide a direct window on the evolution of these ecosystems or their distribution through space and time. However, microbial deposits also produce copious amounts of organic matter, which may be used to decipher any microbial-related origin within the sedimentary record. Microbial mats and biofilms were identified as the potential source of organic material in addition to the surrounding mangrove, soils and suspended particulate matter (SPM). The origin and evolution of the sedimentary organic matter preserved within the lagoonal sediments has been analysed using geochemical parameters such as elemental (TOC, TN and [C/N]_atomic ratio) and isotopic (δ¹³C_org and δ¹⁵N_TN) signals on four sedimentary cores retrieved from different locations in the lagoon and compared with the geochemical signatures of the potential sources. Despite the high potential for organic matter accumulation in the studied lagoon, the TOC and TN downcore values in sediments that were analysed (i.e., micritic muds and bioclastic sands) remain very low compared to the sediment-water interface. The relative contributions of the different potential sources of organic matter were estimated using [C/N]_atomic ratios and δ¹³C_org values. The δ¹⁵N_TN signature was discarded as a source signature as it records synsedimentary, early diagenetic, secondary evolution of the nitrogen signal associated with OM remineralisation (i.e., denitrification). Finally, among the microbial deposits, the slime recognised in the permanently submersed zone of the waterbody appears to be the main contributor to the organic matter preserved within the sediments of the lagoon. SPM, mainly composed of microbial-rich particles, also contribute and cannot be ruled out as a source. Full article

Near-surface diagenesis has been studied in the Langhian siliciclastic rocks of the Montjuïc Hill (Barcelona Plain) by means of petrographical (optical and cathodoluminescence) and geochemical (electron microprobe, δ¹⁸O, δ¹³C, δ³⁴S and ⁸⁷Sr/⁸⁶Sr) analyses. In the hill, these rocks are affected by strong silicification, but the same unit remains non-silicified at depth. The results reveal that fracturing took place after lithification and during uplift. Fracture cementation is clearly controlled by the previous diagenesis of the host rock. In non-silicified areas, cementation is dominated by calcite, which precipitated from meteoric waters. In silicified areas, fractures show multiepisodic cementation produced firstly by barite and secondly by silica, following the sequence opal, lussatite, chalcedony, and quartz. Barite precipitated only in fractures from the mixing of upflowing seawater and percolating meteoric fluids. The presence of silica stalactites, illuviation, and geopetal structures, and δ¹⁸O values indicate that silica precipitation occurred in the vadose regime from low-temperature percolating meteoric fluids, probably during a glacial period. Moreover, the presence of alunite suggests that silica cement formed under acidic conditions. Karst features (vugs and caverns), formed by arenisation, reveal that silica was derived from the dissolution of surrounding silicified host rocks. Full article

Profound knowledge of the structure and texture of rocks and ores as well as the behavior of the materials under external loads is essential to further improvements in size reduction processes, particularly in terms of liberation size. New analytical methods such as computer tomography (CT) were adopted to improve the understanding of material characteristics in rocks and ores relevant to mineral processing, particular the crushing and grinding and the modelling/simulation thereof. Results obtained on the texture and structure of identical samples of rather different rocks and ores (copper ore, granodiorite, kimberlite) are compared by CT with quantitative results from traditional optical microscopy obtained by quantitative microstructural analysis (QMA). While the two approaches show a good agreement of the results in many areas, the measurements with the two different methods also exhibit remarkable differences in other areas, which are discussed further. In conclusion, both methods have their specific advantages starting from sample preparation to the accuracy of information obtained concerning certain parameters of mode and fabric. While sample preparation is faster with CT and information on special distribution of metal minerals is more reliable, the information on mode, grain size and clustering seem to be more precise with QMA. Based on the results, it can be concluded that both methods are comparable in many areas, but in in the field of spatial distribution, they are merely complementary. Full article

The Camarasa Dam was built in 1920 using dolomitic aggregate and Portland cement with two different compositions: type A (dolomite and Portland cement) and type B (dolomite and sand-cement). The sand cement was a finely powdered mixture of dolomite particles and clinker of Portland cement. The mineralogy of concrete was studied by optical microscopy, scanning electron microscopy, and x-ray powder diffraction. Reaction of dedolomitization occurred in the two types of concrete of the Camarasa Dam, as demonstrated by the occurrence of calcite, brucite, and/or absence of portlandite. In the type A concrete, calcite, brucite, and a serpentine-group mineral precipitated as a rim around the dolomite grains and in the paste. The rims, a product of the dedolomitization reaction, protected the surface of dolomite from the dissolution process. In type B concrete, in addition to dolomite and calcite, quartz and K-feldspar were present. Brucite occurred in lower amounts than in the type A concrete as fibrous crystals randomly distributed in the sand-cement paste. Although brucite content was higher in the type A concrete, type B showed more signs of loss of durability. This can be attributed to the further development of the alkali-silica reaction in this concrete type. Full article

Surface roughness has an important influence on the wettability of particles. This paper is an innovative exploration to control the surface wettability of apatite and dolomite from the perspective of roughness in the background of phosphate flotation. Roughness characteristics of apatite and dolomite particles and its effects on wettability were investigated with surface roughness, contact angle measurements, and SEM analysis. The relationship between surface energy and wettability of different roughness surfaces was also discussed. The results indicated that the influence of roughness on apatite and dolomite particles showed the same regularity, and wettability increased with the increasing roughness for hydrophilic surfaces, while the wettability decreased for hydrophobic surfaces. The influence of roughness on wettability can be well explained by Wenzel and Cassie models, and the surface energy of different rough surfaces had a strong correlation with their wettability. When sodium oleate was added after acid treatment, the apatite was hydrophilic, while the dolomite was hydrophobic; the difference in wettability between them became greater as surface roughness increased. Thus, it can be predicted that the selective separation of dolomite and apatite under acid reverse flotation conditions can be strengthened by increasing the mineral surface roughness during comminution. Full article

Predictive modelling of mineral prospectivity, a critical, but challenging procedure for delineation of undiscovered prospective targets in mineral exploration, has been spurred by recent advancements of spatial modelling techniques and machine learning algorithms. In this study, a set of machine learning methods, including random forest (RF), support vector machine (SVM), artificial neural network (ANN), and a deep learning convolutional neural network (CNN), were employed to conduct a data-driven W prospectivity modelling of the southern Jiangxi Province, China. A total of 118 known W occurrences derived from long-term exploration of this brownfield area and eight evidential layers of multi-source geoscience information related to W mineralization constituted the input datasets. This provided a data-rich foundation for training machine learning models. The optimal configuration of model parameters was trained by a grid search procedure and validated by 10-fold cross-validation. The resulting predictive models were comprehensively assessed by a confusion matrix, receiver operating characteristic curve, and success-rate curve. The modelling results indicate that the CNN model achieves the best classification performance with an accuracy of 92.38%, followed by the RF model (87.62%). In contrast, the RF model outperforms the rest of ML models in overall predictive performance and predictive efficiency. This is characterized by the highest value of area under the curve and the steepest slope of success-rate curve. The RF model was chosen as the optimal model for mineral prospectivity in this region as it is the best predictor. The prospective zones delineated by the prospectivity map occupy 9% of the study area and capture 66.95% of the known mineral occurrences. The geological interpretation of the model reveals that previously neglected Mn anomalies are significant indicators. This implies that enrichment of ore-forming material in the host rocks may play an important role in the formation process of wolframite and can represent an innovative exploration criterion for further exploration in this area. Full article

Microinclusions of high-density fluids (HDFs) were studied in coated diamonds from the Udachnaya kimberlite pipe (Siberian craton, Russia). The presence of C-centers in the coats testifies to their formation shortly before kimberlite eruption, whereas the cores have much longer mantle residence in chemically different mantle substrates, i.e., peridotite-type (P-type) and eclogite-type (E-type). The carbon isotope composition indicates an isotopically homogeneous carbon source for coats and a heterogeneous source for cores. Microinclusions in the coats belong to two groups: high-Mg carbonatitic and low-Mg carbonatitic to silicic. A relationship was found between high-Mg carbonatitic HDFs and peridotitic host rocks and between low-Mg carbonatitic to silicic and eclogites. The composition of high-Mg carbonatitic HDFs with a “planed” trace-element pattern can evolve to low-Mg carbonatitic to silicic during percolation through different mantle rocks. The compositional variations of microinclusions in the coats reflect this evolution. Full article

The mineral exploration industry requires new methods and tools to address the challenges of declining mineral reserves and increasing discovery costs. Laser-induced breakdown spectroscopy (LIBS) represents an emerging geochemical tool for mineral exploration that can provide rapid, in situ, compositional analysis and high-resolution imaging in both laboratory and field and settings. We demonstrate through a review of previously published research and our new results how LIBS can be applied to qualitative element detection for geochemical fingerprinting, sample classification, and discrimination, as well as quantitative geochemical analysis, rock characterization by grain size analysis, and in situ geochemical imaging. LIBS can detect elements with low atomic number (i.e., light elements), some of which are important pathfinder elements for mineral exploration and/or are classified as critical commodities for emerging green technologies. LIBS data can be acquired in situ, facilitating the interpretation of geochemical data in a mineralogical context, which is important for unraveling the complex geological history of most ore systems. LIBS technology is available as a handheld analyzer, thus providing a field capability to acquire low-cost geochemical analyses in real time. As a consequence, LIBS has wide potential to be utilized in mineral exploration, prospect evaluation, and deposit exploitation quality control. LIBS is ideally suited for field exploration programs that would benefit from rapid chemical analysis under ambient environmental conditions. Full article

The foamed alkali-activated zeolite materials have been studied primarily in terms of mechanical and structural properties as potential substitutes for concrete and other building materials. However, they also have interesting textural and acid properties that make them much more useful, especially in the chemical industry. The aim of the study is to map in detail the influence of post-synthesis modifications of alkali-activated natural zeolite foams on their chemical, mechanical, and textural properties for possible use in catalytic and adsorption applications. Alkali-activated natural zeolite foam pellets were prepared by activation with mixed potassium hydroxide and sodium silicate activator and foamed using H₂O₂ solution. The foam pellets were post-synthetic modified by leaching with mineral and organic acids and calcination. The properties of the modified materials were characterised on the basis of XRF, XRD, N₂ physisorption, DRIFT, SEM, NH₃-TPD analyses, and the strength measurements. Our data showed that the basic clinoptilolite structure remains unchanged in the material which is stable up to 600 °C after acid leaching. In two-step leaching, the specific surface area increases to 350 m²/g and the leaching process allows the acid properties of the materials to be varied. Full article

This study aims to model grinding of a Polish ferronickel slag and evaluate the particle size distributions (PSDs) of the products obtained after different grinding times. Then, selected products were alkali activated in order to investigate the effect of particle size on the compressive strength of the produced alkali activated materials (AAMs). Other parameters affecting alkali activation, i.e., temperature, curing, and ageing time were also examined. Among the different mathematical models used to simulate the particle size distribution, Rosin–Rammler (RR) was found to be the most suitable. When piecewise regression analysis was applied to experimental data it was found that the particle size distribution of the slag products exhibits multifractal character. In addition, grinding of slag exhibits non-first-order behavior and the reduction rate of each size is time dependent. The grinding rate and consequently the grinding efficiency increases when the particle size increases, but drops sharply near zero after prolonged grinding periods. Regarding alkali activation, it is deduced that among the parameters studied, particle size (and the respective specific surface area) of the raw slag product and curing temperature have the most noticeable impact on the compressive strength of the produced AAMs. Full article

A review and a synthesis of the geological, mineralogical, and crystal chemical data available in the literature on active Spanish bentonitic exploitations were done, and at the same time, new data are provided from a set of representative samples from these deposits. They were located in three different areas with different geological origins: (1) Miocene sedimentary deposits from the Tajo Basin (Madrid–Toledo provinces) in the center of the Iberian Peninsula, where bentonites appear in two different units named for their colors (Green Clays and Pink Clays); (2) samples from Tamame de Sayago (Zamora province) originating from the hydrothermal alteration of granitic Variscan rocks; and 3) Miocene deposits originating from the hydrothermal alteration of volcanic or subvolcanic rocks from the Cabo de Gata volcanic area (Almería Province) in the southern part of Spain, where the three main deposits (Cortijo de Archidona, Los Trancos, and Morrón de Mateo) were studied. The bentonites from the Tajo Basin were formed mainly by trioctahedral smectites, and there were significant mineralogical differences between the Green and Pink Clays, both in terms of the contents of impurities and in terms of smectite crystallochemistry and crystallinity. The smectites from Tamame de Sayago were dioctahedral (montmorillonite–beidellite series), and they appeared with kaolinite, quartz, and mica in all possible proportions, from almost pure bentonite to kaolin. Finally, the compositions of the bentonites from the three studied deposits in Cabo de Gata were quite similar, and zeolites and plagioclases were the main impurities. The structural formulae of the smectites from Cortijo de Archidona and Los Trancos showed a continuous compositional variation in beidellite–montmorillonite, while in Morrón de Mateo, the smectites were mainly montmorillonite, although there was continuous compositional variation from Al montmorillonites to Fe–Mg-rich saponites. The variation in the smectite composition is due to the intrusion of a volcanic dome, which brings new fluids that alter the initial composition of the smectites. Full article

Phlogopite is widely accepted as a major mineral indicator of the modal metasomatism in the upper mantle within a very wide P–T range. The paper reviews data on various phlogopite-forming reactions in upper-mantle peridotites. The review includes both descriptions of naturally occurring reactions and results of experiments that model some of these reactions. Relations of phlogopite with other potassic phases, such as K-richterite, sanidine and K-titanates, are discussed. These data are taken as a basis for thermodynamic modeling of the phlogopite-forming reactions for specific mantle rocks in terms of log(a_H2O) − log(a_K2O) diagrams (pseudosections) using the Gibbs free energy minimization. These diagrams allow estimation of potassium-water activity relations during metasomatic transformations of mantle rocks, prediction sequences of mineral assemblages with respect to these parameters and comparison of metasomatic processes in the rocks of different composition. This approach is illustrated by examples from peridotite xenoliths from kimberlites. Full article

Mineral carbonation is known to be among the most efficient ways to reduce the anthropogenic emissions of carbon dioxide. Serpentine minerals (Mg₃Si₂O₅(OH)₄), have shown great potential for carbonation. A way to improve yield is to thermally activate serpentine minerals prior to the carbonation reaction. This step is of great importance as it controls Mg²⁺ leaching, one of the carbonation reaction limiting factors. Previous studies have focused on the optimization of the thermal activation by determining the ideal activation temperature. However, to date, none of these studies have considered the impacts of the thermal activation on the efficiency of the aqueous-phase mineral carbonation at ambient temperature and moderate pressure in flue gas conditions. Several residence times and temperatures of activation have been tested to evaluate their impact on serpentine dissolution in conditions similar to mineral carbonation. The mineralogical composition of the treated solids has been studied using X-ray diffraction coupled with a quantification using the Rietveld refinement method. A novel approach in order to quantify the meta-serpentine formed during dehydroxylation is introduced. The most suitable mineral assemblage for carbonation is found to be a mixture of the different amorphous phases identified. This study highlights the importance of the mineralogical assemblage obtained during the dehydroxylation process and its impact on the magnesium availability during dissolution in the carbonation reaction. Full article

Effective energy-dispersive X-ray spectroscopy analysis (EDX) with a scanning electron microscope of fine-grained materials (submicrometer scale) is hampered by the interaction volume of the primary electron beam, whose diameter usually is larger than the size of the grains to be analyzed. Therefore, mixed signals of the chemistry of individual grains are expected, and EDX is commonly not applied to such fine-grained material. However, by applying a low primary beam acceleration voltage, combined with a large aperture, and a dedicated mineral classification in the mineral library employed by the Zeiss Mineralogic software platform, mixed signals could be deconvoluted down to a size of 200 nm. In this way, EDX and automated quantitative mineralogy can be applied to investigations of submicrometer-sized grains. It is shown here that reliable quantitative mineralogy and grain size distribution assessment can be made based on an example of fault gouge with a heterogenous mineralogy collected from Ikkattup nunaa Island, southern West Greenland. Full article

The low chromium-to-iron ratio of chromite ores is an important issue in some chromite deposits. The value of the chromite ore is indeed dictated in the market by its iron, as well as its chromium content. In the present study, a chromite concentrate was reprocessed by gravity (spiral concentrator) and magnetic separation to enhance the chromium-to-iron ratio. Also, detailed characterization studies including automated mineralogy were carried out to better understand the nature of the samples. Enhancing the chromium-to-iron ratio was achieved by using advanced spiral separators which will be discussed in this paper. Full article

None of the 40+ equations that have been proposed to describe material properties at the pressures of the Earth’s core and mantle have escaped serious criticism. In this paper, some basic algebraic and thermodynamic constraints are reviewed, with the conclusion that the next step should be a re-examination of the relationship between the dependence of the bulk modulus, K, on pressure, P, that is $K^{\prime }\equiv \mathrm{d}K/dP$ , and the normalized (dimensionless) pressure, $P/K$ . A linear relationship between $1/K^{\prime }$ and $P/K$ terminating at the infinite pressure asymptote, at which these quantities become equal, has been used for analysing properties at extreme pressure, but may be inadequate for calculations requiring precise derivatives of an equation of state. A new analysis indicates that $\mathrm{d}\left(1/K^{\prime }\right)/\mathrm{d}\left(P/K\right)$ increases with compression (or $P/K$ ), but there are, at present, no reliable equations representing this. Relationships between higher derivatives of K and the thermodynamic Grüneisen parameter offer the prospect of a resolution of the problem and hence a new generation of fundamentally-based equations of state. Although an earlier conclusion that a completely general ‘universal’ equation is not possible, in principle, is confirmed in this study, the fundamental relationships present strong constraints for the forms of other proposed equations. Full article

The oxygen (O) and neodymium (Nd) isotopic composition of monazite provides an ideal tracer of metamorphism and hydrothermal activity. Calibration of the matrix effect and monitoring of the external precision of monazite O–Nd isotopes with microbeam techniques, such as secondary ion mass spectrometry (SIMS) and laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICPMS), require well-characterized natural monazite standards for precise microbeam measurements. However, the limited number of standards available is impeding the application of monazite O–Nd isotopes. Here, we report on the RW-1 monazite as a potential new working reference material for microbeam analysis of O–Nd isotopes. Microbeam measurements by electron probe microanalysis (EPMA), SIMS, and LA-MC-ICPMS at 10–24 µm scales have confirmed that it is homogeneous in both elemental and O–Nd isotopic compositions. SIMS measurements yield δ¹⁸O values consistent, within errors, with those obtained by laser fluorination techniques. Precise analyses of Nd isotope by thermal ionization mass spectrometry (TIMS) are consistent with mean results of LA-MC-ICPMS analyses. We recommend δ¹⁸O = 6.30‰ ± 0.16‰ (2SD) and ¹⁴³Nd/¹⁴⁴Nd = 0.512282 ± 0.000011 (2SD) as being the reference values for the RW-1 monazite. Full article

CO₂ hydrates are ice-like solid lattice compounds composed of hydrogen-bonded cages of water molecules that encapsulate guest CO₂ molecules. The formation of CO₂ hydrates in unconsolidated sediments significantly decreases their permeability and increases their stiffness. CO₂ hydrate-bearing sediments can, therefore, act as cap-rocks and prevent CO₂ leakage from a CO₂-stored layer. In this study, we conducted an experimental simulation of CO₂ geological storage into marine unconsolidated sediments. CO₂ hydrates formed during the CO₂ liquid injection process and prevented any upward flow of CO₂. Temperature, pressure, P-wave velocity, and electrical resistance were measured during the experiment, and their measurement results verified the occurrence of the self-trapping effect induced by CO₂ hydrate formation. Several analyses using the experimental results revealed that CO₂ hydrate bearing-sediments have a considerable sealing capacity. Minimum breakthrough pressure and maximum absolute permeability are estimated to be 0.71 MPa and 5.55 × 10⁻⁴ darcys, respectively. Full article

Lithium ion battery (LIB) waste is increasing globally and contains an abundance of valuable metals that can be recovered for re-use. This study aimed to evaluate the recovery of metals from LIB waste leachate using hydrogen sulfide generated by a consortium of sulfate-reducing bacteria (SRB) in a lactate-fed fluidised bed reactor (FBR). The microbial community analysis showed Desulfovibrio as the most abundant genus in a dynamic and diverse bioreactor consortium. During periods of biogenic hydrogen sulfide production, the average dissolved sulfide concentration was 507 mg L⁻¹ and the average volumetric sulfate reduction rate was 278 mg L⁻¹ d⁻¹. Over 99% precipitation efficiency was achieved for Al, Ni, Co, and Cu using biogenic sulfide and NaOH, accounting for 96% of the metal value contained in the LIB waste leachate. The purity indices of the precipitates were highest for Co, being above 0.7 for the precipitate at pH 10. However, the process was not selective for individual metals due to simultaneous precipitation and the complexity of the metal content of the LIB waste. Overall, the process facilitated the production of high value mixed metal precipitates, which could be purified further or used as feedstock for other processes, such as the production of steel. Full article

The present study applied LA–ICP-MS on gem-quality emeralds from the most important sources (Afghanistan, Brazil, Colombia, Ethiopia, Madagascar, Russia, Zambia and Zimbabwe). It revealed that emeralds from Afghanistan, Brazil, Colombia and Madagascar have a relatively lower lithium content (⁷Li < 200 ppmw) compared to emeralds from other places (⁷Li > 250 ppmw). Alkali element contents as well as scandium, manganese, cobalt, nickel, zinc and gallium can further help us in obtaining accurate origin information for these emeralds. UV-Vis spectroscopy can aid in the separation of emeralds from Colombia and Afghanistan from these obtained from the other sources as the latter present pronounced iron-related bands. Intense Type-II water vibrations are observed in the infrared spectra of emeralds from Madagascar, Zambia and Zimbabwe, as well as in some samples from Afghanistan and Ethiopia, which contain higher alkali contents. A band at 2818 cm⁻¹, supposedly attributed to chlorine, was observed only in emeralds from Colombia and Afghanistan. Samples with medium to high alkalis from Ethiopia, Madagascar, Zambia and Zimbabwe can also be separated from the others by Raman spectroscopy based on the lower or equal relative intensity of the Type I water band at around 3608 cm⁻¹ compared to the Type II water band at around 3598 cm⁻¹ band (with some samples from Afghanistan, Brazil and Russia presenting equal relative intensities). Full article

We have determined the Hf isotopic compositions of 12 samples associated with the giant El Teniente Cu-Mo megabreccia deposit, central Chile. The samples range in age from ≥8.9 to 2.3 Ma and provide information about the temporal evolution of their magmatic sources from the Late Miocene to Pliocene. Together with previously published data, the new analysis indicates a temporal decrease of 10 ε_Hf(t) units, from +11.6 down to +1.6, in the 12.7 m.y. from 15 to 2.3 Ma. These variations imply increasing incorporation of continental crust through time in the magmas that formed these rocks. The fact that the samples include mantle-derived olivine basalts and olivine lamprophyres suggests that these continental components were incorporated into their mantle source, and not by intra-crustal contamination (MASH). We attribute the increase, between the Middle Miocene and Pliocene, of crustal components in the subarc mantle source below El Teniente to be due to increased rates of subduction erosion and transport of crust into the mantle. The deposit formed above a large, long-lived, vertically zoned magma chamber that developed due to compressive deformation and persisted between ~7 to 4.6 Ma. Progressively more hydrous mantle-derived mafic magmas feed this chamber from below, providing heat, H₂O, S and metals, but no unique “fertile” Cu-rich magma was involved in the formation of the deposit. As the volume of these mantle-derived magmas decreased from the Late Miocene into the Pliocene, the chamber crystallized and solidified, producing felsic plutons and large metal-rich magmatic-hydrothermal breccias that emplaced Cu and S into the older (≥8.9 Ma) mafic host rocks of this megabreccia deposit. Full article

Polymineralic inclusions in megacrysts have been reported to occur in kimberlites worldwide. The inclusions are likely the products of early kimberlite melt(s) which invaded the pre-existing megacryst minerals at mantle depths (i.e., at pressures ranging from 4 to 6 GPa) and crystallized or quenched upon emplacement of the host kimberlite. The abundance of carbonate minerals (e.g., calcite, dolomite) and hydrous silicate minerals (e.g., phlogopite, serpentine, chlorite) within polymineralic inclusions suggests that the trapped melt was more volatile-rich than the host kimberlite now emplaced in the crust. However, the exact composition of this presumed early kimberlite melt, including the inventory of trace elements and volatiles, remains to be more narrowly constrained. For instance, one major question concerns the role of accessory alkali-halogen-phases in polymineralic inclusions, i.e., whether such phases constitute a common primary feature of kimberlite melt(s), or whether they become enriched in late-stage differentiation processes. Recent studies have shown that polymineralic inclusions react with their host minerals during ascent of the kimberlite, while being largely shielded from processes that affect the host kimberlite, e.g., the assimilation of xenoliths (mantle and crustal), degassing of volatiles, and secondary alteration. Importantly, some polymineralic inclusions within different megacryst minerals were shown to preserve fresh glass. A major conclusion of this review is that the abundance and mineralogy of polymineralic inclusions are directly influenced by the physical and chemical properties of their host minerals. When taking the different interactions with their host minerals into account, polymineralic inclusions in megacrysts can serve as useful proxies for the multi-stage origin and evolution of kimberlite melt/magma, because they can (i) reveal information about primary characteristics of the kimberlite melt, and (ii) trace the evolution of kimberlite magma on its way from the upper mantle to the crust. Full article