Editor’s Choice Articles

Silicocarbonate pegmatites from the southern Grenville Province have provided exceptionally large crystal specimens for more than a century. Their mineral parageneses include euhedral calc–silicate minerals such as amphibole, clinopyroxene, and scapolite within a calcite matrix. Crystals can reach a meter or more in long dimension. Minor and locally abundant phases reflect local bedrock compositions and include albite, apatite, perthitic microcline, phlogopite, zircon, tourmaline, titanite, danburite, uraninite, sulfides, and many other minerals. Across the Adirondack Region, individual exposures are of limited aerial extent (<10,000 m²), crosscut metasedimentary rocks, especially calc–silicate gneisses and marbles, are undeformed and are spatially and temporally associated with granitic pegmatites. Zircon U–Pb results include both Shawinigan (circa 1165 Ma) and Ottawan (circa 1050 Ma) intrusion ages, separated by the Carthage-Colton shear zone. Those of Shawinigan age (Lowlands) correspond with the timing of voluminous A-type granitic magmatism, whereas Ottawan ages (Highlands) are temporally related to orogenic collapse, voluminous leucogranite and granitic pegmatite intrusion, iron and garnet ore development, and pervasive localized hydrothermal alteration. Inherited zircon, where present, reflects the broad range of igneous and detrital ages of surrounding rocks. Carbon and oxygen isotopic ratios from calcite plot within a restricted field away from igneous carbonatite values to those of typical sedimentary carbonates and local marbles. Collectively, these exposures represent a continuum between vein-dyke and skarn occurrences involving the anatexis of metasedimentary country rocks. Those of Ottawan age can be tied to movement and fluid flow along structures accommodating orogenic collapse, particularly the Carthage-Colton shear zone. Full article

The increasing demand for green technology and battery metals necessitates a review of geological exploration techniques for Li–Cs–Ta (LCT) pegmatites, which is applicable to the work of mining companies. This paper reviews the main controls of LCT pegmatite genesis relevant to mineral exploration programs and presents a workflow of grassroots exploration techniques, supported by examples from central Europe and Africa. Geological exploration commonly begins with information gathering, desktop studies and Geographic Information System (GIS) data reviews. Following the identification of prospective regional areas, initial targets are verified in the field by geological mapping and geochemical sampling. Detailed mineralogical analysis and geochemical sampling of rock, soil and stream sediments represent the most important tools for providing vectors to LCT pegmatites, since the interpretation of mineralogical phases, deportment and liberation characteristics along with geochemical K/Rb, Nb/Ta and Zr/Hf metallogenic markers can detect highly evolved rocks enriched in incompatible elements of economic interest. The importance of JORC (Joint Ore Reserves Committee) 2012 guidelines with regards to obtaining geological, mineralogical and drilling data is discussed and contextualised, with the requirement of treating LCT pegmatites as industrial mineral deposits. Full article

A₁-type granite xenoliths occur in alkali basalts erupted during Pliocene–Pleistocene continental rifting of Carpathian back-arc basin (Central Europe). The Pliocene (5.2 Ma) peraluminous calc-alkalic granite contains unusually high concentrations of critical metals bound in Nb, Ta, REE, U, Th-oxides typical for silica-undersaturated alkalic granites, and syenites: columbite-Mn, fergusonite-Y, oxycalciopyrochlore, Nb-rutile, and Ca-niobate (fersmite or viggezite). In contrast, it does not contain allanite and monazite—the main REE-carriers in calc-alkalic granites. The crystallization of REE-bearing Nb-oxides instead of OH-silicates and phosphates was probably caused by strong water deficiency and low phosphorus content in the parental magma. Increased Nb and Ta concentrations have been inherited from the mafic parental magma derived from the metasomatized mantle. The strong Al- and Ca-enrichment probably reflects the specific composition of the mantle wedge modified by fluids, alkalic, and carbonatitic melts liberated from the subducted slab of oceanic crust prior to the Pliocene-Pleistocene rifting. Full article

Eudialyte-hosted critical metal deposits potentially represent major sources of rare earth elements (REE), zirconium and niobium. Here, we study the chemical and isotopic composition of fresh and altered eudialyte in nepheline syenite from the Ilímaussaq Complex, Greenland, one of the world’s largest known eudialyte-hosted deposits. Late-magmatic hydrothermal alteration caused partial replacement of primary magmatic eudialyte by complex pseudomorph assemblages of secondary Zr-, Nb-, and REE-minerals. Three secondary assemblage types are characterised by the zirconosilicates catapleiite, gittinsite and zircon, respectively, of which the catapleiite type is most common. To investigate elemental exchange associated with alteration and to constrain the nature of the metasomatic fluids, we compare trace elements and Sm/Nd isotope compositions of unaltered eudialyte crystals and their replaced counterparts from five syenite samples (three catapleiite-type, one gittinsite-type, and one zircon-type assemblage). Trace element budgets for the catapleiite-type pseudomorphs indicate a 15–30% loss of REE, Ta, Nb, Zr, Sr and Y relative to fresh eudialyte. Moreover, the gittinsite- and zircon-type assemblages record preferential heavy REE (HREE) depletion (≤50%), suggesting that the metasomatic fluids mobilised high field strength elements. Initial Nd isotope ratios of unaltered eudialyte and catapleiite- and gittinsite-type pseudomorphs are indistinguishable, confirming a magmatic fluid origin. However, a higher initial ratio and stronger HREE depletion in the zircon-type pseudomorphs suggests a different source for the zircon-forming fluid. Although alteration reduces the metal budget of the original eudialyte volume, we infer that these elements re-precipitate nearby in the same rock. Alteration, therefore, might have little effect on overall grade but preferentially separates heavy and light REE into different phases. Targeted processing of the alteration products may access individual rare earth families (heavy vs. light) and other metals (Zr, Nb, Ta) more effectively than processing the fresh rock. Full article

The large-scale Maoping W–Sn deposit in the Gannan metallogenic belt of the eastern Nanling Range, South China, spatially associated with the Maoping granite pluton, hosts total ore reserves of 103,000 t WO₃ and 50,000 t Sn. Two different types of mineralization developed in this deposit: Upper quartz vein-type mineralization, mostly within the Cambrian metamorphosed sandstone and slate, and underneath greisen-type mineralization within the Maoping granite. Cassiterites from both types of mineralization coexist with wolframite. Here we report for the first time in situ U–Pb data on cassiterite and zircon of the Maoping deposit obtained by LA-ICP-MS. Cassiterite from quartz vein and greisen yielded weighted average ²⁰⁶Pb/²³⁸U ages of 156.8 ± 1.5 Ma and 156.9 ± 1.4 Ma, respectively, which indicates that the two types of mineralization formed roughly at the same time. In addition, the two mineralization ages are consistent with the emplacement age of the Maoping granite (159.0 ± 1.5 Ma) within error, suggesting a close temporal and genetic link between W–Sn mineralization and granitic magmatism. The two types of mineralization formed at the same magmatic-hydrothermal event. Cassiterite from both types of mineralization shows high Fe, Ta, and Zr contents with a low Zr/Hf ratio, suggesting that the ore-forming fluid should be derived from the highly differentiated Maoping granite pluton. Cassiterite in greisen has higher contents of Nb and Ta but a lower concentration of Ti compared with that in quartz vein, indicating that the formation temperature of greisen-type mineralization is little higher than that of quartz-vein-type mineralization. Full article

Iron control in the atmospheric acid leaching (AL) of nickel laterite was evaluated in this study. The aim was to decrease acid consumption and iron dissolution by iron precipitation during nickel leaching. The combined acid leaching and iron precipitation process involves direct acid leaching of the limonite type of laterite followed by a simultaneous iron precipitation and nickel leaching step. Iron precipitation as jarosite is carried out by using nickel containing silicate laterite for neutralization. Acid is generated in the jarosite precipitation reaction, and it dissolves nickel and other metals like magnesium from the silicate laterite. Leaching tests were carried out using three laterite samples from the Agios Ioannis, Evia Island, and Kastoria mines in Greece. Relatively low acid consumption was achieved during the combined precipitation and acid leaching tests. The acid consumption was approximately 0.4 kg acid per kg laterite, whereas the acid consumption in direct acid leaching of the same laterite samples was approximately 0.6–0.8 kg acid per kg laterite. Iron dissolution was only 1.5–3% during the combined precipitation and acid leaching tests, whereas in direct acid leaching it was 15–30% with the Agios Ioannis and Evia Island samples and 80% with the Kastoria sample. Full article

Chromium-bearing tourmalines are rare. Chromium-rich tourmaline from the northwestern part of the Adirondack Mountains in the Adirondack Lowlands is among the most chromium-rich tourmalines found to date. The mineral, with >21.0 wt. % Cr₂O₃, is from the marble-hosted talc–tremolite–cummingtonite schist in the #1 mine in Balmat, St. Lawrence County, New York. The atomic arrangement of the sample (a = 16.0242(3) Å, c = 7.3002(2) Å) was refined to R1 = 0.0139. The composition, from chemical analyses and optimization of the formula, is ^X(Ca_0.22Na_0.69K_0.01) ^Y(Cr³⁺_1.68Mg_0.80Ti_0.13V_0.06Mn_0.02Fe_0.02Li_0.29) ^Z(Al_3.11Cr³⁺_1.18Mg_1.70Fe_0.01) ^T(Si_5.93Al_0.07) B₃O₂₇ OH_3.99 F_0.01. There has been extensive debate over the ordering of Cr³⁺ between the tourmaline Y and Z octahedral sites. Recent work has suggested that, at low concentrations (<~1.03 apfu), the substituent Cr³⁺ is ordered into the Y-site, whereas, at greater concentrations, the substituent is disordered over both octahedral sites. An analysis of nine recently published, high-precision structures of chromium-bearing tourmaline, in combination with the Adirondack tourmaline, suggests that structural changes to the Y-site at low concentrations of Cr³⁺ induce changes in the Z-site that make it more amenable to incorporation of the Cr³⁺ substituents by increasing <Z–O>. The bond lengths change to lower the bond-valence sum of Cr³⁺ in the Z-site of the chromium-dravite, making that site more amenable to the substituent. Calculations suggest that the Z-site begins to accept substituent Cr³⁺ when the bond valence sum of that ion in Z reduces to a value of ~3.36 valence units. Full article

From 1964 to the early 1970s, Orson Anderson led a research program at the Lamont Geological Observatory in the newly-emerging field of “mineral physics”. In collaboration with colleagues Edward Schreiber and Naohiro Soga, Orson exploited the techniques of physical acoustics to study the behavior of the sound velocities of minerals at elevated pressures and temperatures. This research program also included semi-empirical studies of the relationships between the bulk modulus and the molar volume of solids, the use of lattice dynamics to calculate the elastic moduli of cubic structures as a function of pressure to predict instabilities, and theoretical investigations of the Lagrangian and Eulerian formulations of finite strain equations of state. Full article

Variations in clay mineral assemblages have been widely used to understand changes in sediment provenance during glacial and interglacial periods. Smectite clay minerals, however, have a range of various elemental compositions that possibly originated from multiple different sources. Therefore, it might be crucial to distinguish the various types of smectites by analyzing their elemental composition in order to verify the sediment provenances with certainty. This hypothesis was tested for the clay mineral characteristics in a marine sediment core from the southern Drake Passage (GC05-DP02). Rare earth elements and ${\mathsf{\epsilon }}_{Nd}$ data had previously indicated that fine grained detritus was supplied from the Weddell Sea to the core site during interglacial periods, when the sediments contained more Al-rich smectite (montmorillonite). Indeed, marine sediments collected close to the Larsen Ice Shelf on the eastern Antarctic Peninsula continental shelf, western Weddell Sea embayment, show more Al-rich smectite components as compared with other possible West Antarctic sources, such as the Ross Sea embayment or King George Island, South Shetland Islands. Furthermore, two types of smectite (Al-rich and Al-poor) were identified in core GC360 from the Bellingshausen Sea shelf, suggesting that during glacial periods some sediment is derived from subglacial erosion of underlying pre-Oligocene sedimentary strata containing predominantly Al-rich montmorillonite. This finding reveals different sources for smectites in sediments deposited at site GC360 during the last glacial period and during the present interglacial that show only minor differences in smectite contents. For the interglacial period, two groups of smectite with a wide range of Al-rich and Mg–Fe-rich were identified, which indicate delivery from two different sources: (1) the detritus with high contents of Mg–Fe-rich smectite supplied from Beethoven Peninsula, southwestern Alexander island and (2) the detritus with higher contents of Al-rich smectite (montmorillonite) possibly derived from the subglacial reworking of pre-Oligocene sedimentary strata. These results demonstrate that the elemental compositions of smectites can be used to differentiate the sources of smectites in marine sediments, which is an important tool to define sediment provenance in detail, when down-core changes observed in clay mineral assemblages are interpreted. Full article

One-class support vector machine (OCSVM) is an efficient data-driven mineral prospectivity mapping model. Since the parameters of OCSVM directly affect the performance of the model, it is necessary to optimize the parameters of OCSVM in mineral prospectivity mapping. Trial and error method is usually used to determine the “optimal” parameters of OCSVM. However, it is difficult to find the globally optimal parameters by the trial and error method. By combining OCSVM with the bat algorithm, the intialization parameters of the OCSVM can be automatically optimized. The combined model is called bat-optimized OCSVM. In this model, the area under the curve (AUC) of OCSVM is taken as the fitness value of the objective function optimized by the bat algorithm, the value ranges of the initialization parameters of OCSVM are used to specify the search space of bat population, and the optimal parameters of OCSVM are automatically determined through the iterative search process of the bat algorithm. The bat-optimized OCSVMs were used to map mineral prospectivity of the Helong district, Jilin Province, China, and compared with the OCSVM initialized by the default parameters (i.e., common OCSVM) and the OCSVM optimized by trial and error. The results show that (a) the receiver operating characteristic (ROC) curve of the trial and error-optimized OCSVM is intersected with those of the bat-optimized OCSVMs and (b) the ROC curves of the optimized OCSVMs slightly dominate that of the common OCSVM in the ROC space. The area under the curves (AUCs) of the common and trial and error-optimized OCSVMs (0.8268 and 0.8566) are smaller than those of the bat-optimized ones (0.8649 and 0.8644). The optimal threshold for extracting mineral targets was determined by using the Youden index. The mineral targets predicted by the common and trial and error-optimized OCSVMs account for 29.61% and 18.66% of the study area respectively, and contain 93% and 86% of the known mineral deposits. The mineral targets predicted by the bat-optimized OCSVMs account for 19.84% and 14.22% of the study area respectively, and also contain 93% and 86% of the known mineral deposits. Therefore, we have 0.93/0.2961 = 3.1408 < 0.86/0.1866 = 4.6088 < 0.93/0.1984 = 4.6875 < 0.86/0.1422 = 6.0478, indicating that the bat-optimized OCSVMs perform slightly better than the common and trial and error-optimized OCSVMs in mineral prospectivity mapping. Full article

The Huari Huari deposit, Potosí Department in SW Bolivia, hosts polymetallic stratiform and vein mineralization of Miocene age with significant concentrations of the critical metal indium (In). Vein mineralization records document early crystallization of quartz and cassiterite followed by prominent associations of sulfides and sulfosalts. The earliest sulfide was arsenopyrite, followed by pyrrhotite, and progressively giving way to pyrite as the main iron sulfide, whereas Cu–Ag–Pb sulfosalts constitute late hypogene associations. Sphalerite is the chief ore mineral, and its crystallization is extended during most of the mineralization lifespan as evidenced by its initial cocrystallization with pyrrhotine, then with pyrite, and finally with Ag–Pb sulfosalts. The composition of sphalerite varies from early to late generations with a continuous decrease in FeS that attests to a decrease in temperature, which is constrained to vary from ~450 to <200 °C, and/or an increase in f(S₂), both congruent with the described paragenetic sequence. Indium concentrated mostly in the structure of Fe-rich sphalerite (up to 3.49 wt. %) and stannite (up to 2.64 wt. %) as limited solid solutions with roquesite in the (Zn,Fe)S–Cu₂FeSnS₄–CuInS₂ pseudoternary system. In sphalerite, In shows a strong positive correlation with Cu at Cu/In = 1, suggesting its incorporation via a (Cu⁺ + In³⁺) ↔ 2Zn²⁺ coupled substitution, and it does not correlate with Fe. In stannite, In shows a moderate, negative correlation with Cu and Sn, and an In³⁺ ↔ (Cu⁺ + ½ Sn⁴⁺) coupled substitution is suggested. Coexisting sphalerite and stannite yielded the highest In concentrations and crystallized at temperatures between 350 and 250 °C. Copper activity probably played a major role in the accumulation of In in the structure of sphalerite since In-bearing sphalerite coexisted with the deposition of stannite, shows high concentrations of Cu (up to 0.13 atoms per formula unit (a.p.f.u.)) in its structure, and hosts exsolutions of stannite and chalcopyrite. Distribution on the district scale of In suggests an input of hydrothermal fluids richer in Cu in the central position of the mineralizing system, represented by the Antón Bravo vein. Full article

A traditional hydrocyclone can only generate two products with different size fractions after one classification, which does not meet the fine classification requirements for narrow size fractions. In order to achieve the fine classification, a multi-product hydrocyclone with double-overflow-pipe structure was designed in this study. In this work, numerical simulation and experimental test methods were used to study the internal flow field characteristics and distribution characteristics of the product size fraction. The simulation results showed that in contrast with the traditional single overflow pipe, there were two turns in the internal axial velocity direction of the hydrocyclone with the double-overflow-pipe structure. Meanwhile, the influence rule of the diameter of the underflow outlet on the flow field characteristics was obtained through numerical simulation. From the test, five products with different size fractions were obtained after one classification and the influence rule of the diameter of the underflow outlet on the size fraction distribution of multi-products was also obtained. This work provides a feasible research idea for obtaining the fine classification of multiple products. Full article

Municipal solid waste incineration bottom ash (MSWI BA) is the main output of the municipal solid waste incineration process, both in mass and volume. It contains some heavy metals that possess market value, but may also limit the utilization of the material. This study illustrates a robust and simple heap leaching method for recovering zinc and copper from MSWI BA. Moreover, the effect of autotrophic and acidophilic bioleaching microorganisms in the system was studied. Leaching yields for zinc and copper varied between 18–53% and 6–44%, respectively. For intensified copper dissolution, aeration and possibly iron oxidizing bacteria caused clear benefits. The MSWI BA was challenging to treat. The main components, iron and aluminum, dissolved easily and unwantedly, decreasing the quality of pregnant leach solution. Moreover, the physical nature and the extreme heterogeneity of the material caused operative requirements for the heap leaching. Nevertheless, with optimized parameters, heap leaching may offer a proper solution for MSWI BA treatment. Full article

The Jiaodong Peninsula in eastern China is the third largest gold-mining area and one of the most important orogenic gold provinces in the world. Ore shoots plunging in specific orientations are a ubiquitous feature of the Jiaodong lode deposits. The Sizhuang gold deposit, located in northwestern Jiaodong, is characterized by orebodies of different occurrences. The orientation of ore shoots has remained unresolved for a long time. In this paper, geostatistical tools were used to determine the plunge and structural control of ore shoots in the Sizhuang deposit. The ellipses determined by variogram modeling reveal the anisotropy of mineralization, plus the shape, size, and orientation of individual ore shoots. The long axes of the anisotropy ellipses trend NE or SEE and plunge 48° NE down the dip. However, individual ore shoots plunge almost perpendicular to the plunge of the ore deposit as a whole. This geometry is interpreted to have resulted from two periods of fluid flow parallel to two sets of striations that we identified on ore-controlling faults. Thrust-related lineations with a sinistral strike-slip component were associated with early-stage mineralization. This was overprinted by dextral and normal movement of the ore-controlling fault that controlled the late-stage mineralization. This kinematic switch caused a change in the upflow direction of ore-forming fluid, which in turn controlled the orientation of the large-scale orebodies and the subvertical plunge of individual ore shoots. Thus, a regional transition from NW-to-SE-trending compression to NW-to-SE-trending extension is interpreted as the geodynamic background of the ore-forming process. This research exemplifies an effective exploration strategy for studying the structural control of the geometry, orientation, and grade distribution of orebodies via the integration of geostatistical tools and structural analysis. Full article

Rare earth elements (REE) are essential raw materials used in modern technology. Current production of REE is dominated by hard-rock mining, particularly in China, which typically requires high energy input. In order to expand the resource base of the REE, it is important to determine what alternative sources exist. REE placers have been known for many years, and require less energy than mining of hard rock, but the REE ore minerals are typically derived from eroded granitic rocks and are commonly radioactive. Other types of REE placers, such as those derived from volcanic activity, are rare. The Aksu Diamas heavy mineral placer in Turkey has been assessed for potential REE extraction as a by-product of magnetite production, but its genesis was not previously well understood. REE at Aksu Diamas are hosted in an array of mineral phases, including apatite, chevkinite group minerals (CGM), monazite, allanite and britholite, which are concentrated in lenses and channels in unconsolidated Quaternary sands. Fingerprinting of pyroxene, CGM, magnetite and zircon have identified the source of the placer as the nearby Gölcük alkaline volcanic complex, which has a history of eruption throughout the Plio-Quaternary. Heavy minerals were eroded from tephra and reworked into basinal sediments. This type of deposit may represent a potential resource of REE in other areas of alkaline volcanism. Full article

The main advantage of X-ray microcomputed tomography (µCT) as a non-destructive imaging tool lies in its ability to analyze the three-dimensional (3D) interior of a sample, therefore eliminating the stereological error exhibited in conventional two-dimensional (2D) image analysis. Coupled with the correct data analysis methods, µCT allows extraction of textural and mineralogical information from ore samples. This study provides a comprehensive overview on the available and potentially useful data analysis methods for processing 3D datasets acquired with laboratory µCT systems. Our study indicates that there is a rapid development of new techniques and algorithms capable of processing µCT datasets, but application of such techniques is often sample-specific. Several methods that have been successfully implemented for other similar materials (soils, aggregates, rocks) were also found to have the potential to be applied in mineral characterization. The main challenge in establishing a µCT system as a mineral characterization tool lies in the computational expenses of processing the large 3D dataset. Additionally, since most of the µCT dataset is based on the attenuation of the minerals, the presence of minerals with similar attenuations limits the capability of µCT in mineral segmentation. Further development on the data processing workflow is needed to accelerate the breakthrough of µCT as an analytical tool in mineral characterization. Full article

The role of post-magmatic processes in the composition of chromitites hosted in ophiolite complexes, the origin of super-reduced phases, and factors controlling the carbon recycling in a supra-subduction zone environment are still unclear. The present contribution compiles the first scanning electron microscope/energy-dispersive (SEM/EDS) data on graphite-like amorphous carbon, with geochemical and mineral chemistry data, from chromitites of the Skyros, Othrys, Pindos, and Veria ophiolites (Greece). The aim of this study was the delineation of potential relationships between the modified composition of chromite and the role of redox conditions, during the long-term evolution of chromitites in a supra-subduction zone environment. Chromitites are characterized by a strong brittle (cataclastic) texture and the presence of phases indicative of super-reducing phases, such as Fe–Ni–Cr-alloys, awaruite (Ni₃Fe), and heazlewoodite (Ni₃S₂). Carbon-bearing assemblages are better revealed on Au-coated unpolished sections. Graphite occurs in association with hydrous silicates (chlorite, serpentine) and Fe²⁺-chromite, as inclusions in chromite, filling cracks within chromite, or as nodule-like graphite aggregates. X-ray spectra of graphite–silicate aggregates showed the presence of C, Si, Mg, Al, O in variable proportions, and occasionally K and Ca. The extremely low fO₂ during serpentinization facilitated the occurrence of methane in microfractures of chromitites, the precipitation of super-reducing phases (metal alloys, awaruite, heazlewoodite), and graphite. In addition, although the origin of Fe–Cu–Ni-sulfides in ultramafic parts of ophiolite complexes is still unclear, in the case of the Othrys chromitites, potential reduction-induced sulfide and/or carbon saturation may drive formation of sulfide ores and graphite-bearing chromitites. The presented data on chromitites covering a wide range in platinum-group element (PGE) content, from less than 100 ppb in the Othrys to 25 ppm ΣPGE in the Veria ores, showed similarity in the abundance of graphite-like carbon. The lack of any relationship between graphite (and probably methane) and the PGE content may be related to the occurrence of the (Ru–Os–Ir) minerals in chromitites, which occur mostly as oxides/hydroxides, and to lesser amounts of laurite, with pure Ru instead activating the stable CO₂ molecule and reducing it to methane (experimental data from literature). Full article

Demand for high-quality iron concentrate is significantly increasing around the world. Thus, the development of the techniques for a selective separation and rejection of typical associated minerals in the iron oxide ores, such as phosphorous minerals (mainly apatite group), is a high priority. Reverse anionic flotation by using sodium silicate (SS) as an iron oxide depressant is one of the techniques for iron ore processing. This investigation is going to present a synthesized reagent “sodium co-silicate (SCS)” for hematite depression through a reverse anionic flotation. The main hypothesis is the selective depression of hematite and, simultaneously, modification of the pulp pH by SCS. Various flotation experiments, including micro-flotation, and batch flotation of laboratory and industrial scales, were conducted in order to compare the depression selectivity of SS versus SCS. Outcomes of flotation tests at the different flotation scales demonstrated that hematite depression by SCS is around 3.3% higher than by SS. Based on flotation experiment outcomes, it was concluded that SCS can modify the pH of the process at ~9.5, and the plant reagents (including NaOH, Na₂CO₃, and SS gel) can be replaced by just SCS, which can also lead to a higher efficiency in the plant. Full article

The Precambrian rocks of the Keivy Terrane reveal five types of carbonaceous matter (CM): Fine-grained, flaky, nest, vein, and spherulitic. These types differ in their distribution character, carbon isotope composition, and graphitization temperatures calculated by the Raman spectra of carbonaceous material (RSCM) geothermometry. Supracrustal rocks of the Keivy Terrane contain extremely isotopically light (δ¹³C_PDB = –43 ± 3‰) carbon. Presumably, its source was a methane–aqueous fluid. According to temperature calculations, this carbon matter and the host strata underwent at least two stages of metamorphism in the west of the Keivy Terrane and one stage in the east. The CM isotope signatures of several samples of kyanite schists (δ¹³C_PDB = –33 ± 5‰) are close to those of oils and oil source rocks, and they indicate an additional carbon reservoir. Thus, in the Keivy territory, an oil-and-gas bearing basin has existed. Heavy carbon (δ¹³C_PDB = −8 ± 3‰) precipitated from an aqueous CO₂-rich fluid is derived from either the lower crust or the mantle. This fluid probably migrated from the Keivy alkaline granites into the surrounding rocks previously enriched with “methanogenic” carbon. Full article

Six orogenic gold deposits constitute the Yangshan gold belt in the West Qinling Orogen. Gold is mostly invisible in solid solution or in the sulfide lattice, with minor visible gold associated with stibnite and in quartz-calcite veins. Detailed textural and trace-element analysis of sulfides in terms of a newly-erected paragenetic sequence for these deposits, together with previously published data, demonstrate that early magmatic-hydrothermal pyrite in granitic dike host-rocks has much higher Au contents than diagenetic pyrite in metasedimentary host rocks, but lower contents of As, Au, and Cu than ore-stage pyrite. Combined with sulfur isotope data, replacement textures in the gold ores indicate that the auriferous ore-fluids post-dated the granitic dikes and were not magmatic-hydrothermal in origin. There is a strong correlation between the relative activities of S and As and their total abundances in the ore fluid and the siting of gold in the Yangshan gold ores. Mass balance calculations indicate that there is no necessity to invoke remobilization processes to explain the occurrence of gold in the ores. The only exception is the Py_1-2 replacement of Py_1m, where fluid-mediated coupled dissolution-reprecipitation reactions may have occurred to exchange Au between the two pyrite phases. Full article

In this study, the oxygen isotope (δ¹⁸O) composition of pink to red gem-quality rubies from Paranesti, Greece was investigated using in-situ secondary ionization mass spectrometry (SIMS) and laser-fluorination techniques. Paranesti rubies have a narrow range of δ¹⁸O values between ~0 and +1‰ and represent one of only a few cases worldwide where δ¹⁸O signatures can be used to distinguish them from other localities. SIMS analyses from this study and previous work by the authors suggests that the rubies formed under metamorphic/metasomatic conditions involving deeply penetrating meteoric waters along major crustal structures associated with the Nestos Shear Zone. SIMS analyses also revealed slight variations in δ¹⁸O composition for two outcrops located just ~500 m apart: PAR-1 with a mean value of 1.0‰ ± 0.42‰ and PAR-5 with a mean value of 0.14‰ ± 0.24‰. This work adds to the growing use of in-situ methods to determine the origin of gem-quality corundum and re-confirms its usefulness in geographic “fingerprinting”. Full article

Greece contains several gem corundum deposits set within diverse geological settings, mostly within the Rhodope (Xanthi and Drama areas) and Attico-Cycladic (Naxos and Ikaria islands) tectono-metamorphic units. In the Xanthi area, the sapphire (pink, blue to purple) deposits are stratiform, occurring within marble layers alternating with amphibolites. Deep red rubies in the Paranesti-Drama area are restricted to boudinaged lenses of Al-rich metapyroxenites alternating with amphibolites and gneisses. Both occurrences are oriented parallel to the ultra-high pressure/high pressure (UHP/HP) Nestos suture zone. On central Naxos Island, colored sapphires are associated with desilicated granite pegmatites intruding ultramafic lithologies (plumasites), occurring either within the pegmatites themselves or associated metasomatic reaction zones. In contrast, on southern Naxos and Ikaria Islands, blue sapphires occur in extensional fissures within Mesozoic metabauxites hosted in marbles. Mineral inclusions in corundums are in equilibrium and/or postdate corundum crystallization and comprise: spinel and pargasite (Paranesti), spinel, zircon (Xanthi), margarite, zircon, apatite, diaspore, phlogopite and chlorite (Naxos) and chloritoid, ilmenite, hematite, ulvospinel, rutile and zircon (Ikaria). The main chromophore elements within the Greek corundums show a wide range in concentration: the Fe contents vary from (average values) 1099 ppm in the blue sapphires of Xanthi, 424 ppm in the pink sapphires of Xanthi, 2654 ppm for Paranesti rubies, 4326 ppm for the Ikaria sapphires, 3706 for southern Naxos blue sapphires, 4777 for purple and 3301 for pink sapphire from Naxos plumasite, and finally 4677 to 1532 for blue to colorless sapphires from Naxos plumasites, respectively. The Ti concentrations (average values) are very low in rubies from Paranesti (41 ppm), with values of 2871 ppm and 509 in the blue and pink sapphires of Xanthi, respectively, of 1263 ppm for the Ikaria blue sapphires, and 520 ppm, 181 ppm in Naxos purple, pink sapphires, respectively. The blue to colorless sapphires from Naxos plumasites contain 1944 to 264 ppm Ti, respectively. The very high Ti contents of the Xanthi blue sapphires may reflect submicroscopic rutile inclusions. The Cr (average values) ranges from 4 to 691 ppm in the blue, purple and pink colored corundums from Naxos plumasite, is quite fixed (222 ppm) for Ikaria sapphires, ranges from 90 to 297 ppm in the blue and pink sapphires from Xanthi, reaches 9142 ppm in the corundums of Paranesti, with highest values of 15,347 ppm in deep red colored varieties. Each occurrence has both unique mineral assemblage and trace element chemistry (with variable Fe/Mg, Ga/Mg, Ga/Cr and Fe/Ti ratios). Additionally, oxygen isotope compositions confirm their geological typology, i.e., with, respectively δ¹⁸O of 4.9 ± 0.2‰ for sapphire in plumasite, 20.5‰ for sapphire in marble and 1‰ for ruby in mafics. The fluid inclusions study evidenced water free CO₂ dominant fluids with traces of CH₄ or N₂, and low CO₂ densities (0.46 and 0.67 g/cm³), which were probably trapped after the metamorphic peak. The Paranesti, Xanthi and central Naxos corundum deposits can be classified as metamorphic sensu stricto (s.s.) and metasomatic, respectively, those from southern Naxos and Ikaria display atypical magmatic signature indicating a hydrothermal origin. Greek corundums are characterized by wide color variation, homogeneity of the color hues, and transparency, and can be considered as potential gemstones. Full article

The crystallization behaviour of jarosite and schwertmannite has been studied by precipitation-aging experiments performed using different parent-solution concentrations at acidic conditions and ambient temperature. Schwertmannite exhibits low crystallinity and is the only mineral identified during low-concentration (LC) experiments. However, in high-concentration (HC) experiments, a relatively rapid Ostwald ripening process leads to the transformation of schwertmannite into natrojarosite. The presence of sodium modifies the morphology and stability of the obtained phases. TEM observations reveal that schwertmannite particles consist of disoriented nanodomains (~6 nm) spread in an amorphous mass. In contrast, natrojarosite particles exhibit a single-domain, highly crystalline core, with the crystallinity decreasing from core to rim. The thermal behaviour of these phases depends on both their composition and their degree of crystallinity. TG and DTG analyses show that, below 500 °C, the amount of structural water is clearly higher in schwertmannite than in natrojarosite. The present results highlight the role of the ripening processes in epigenetic conditions and could be important in interpreting the formation of jarosite in Earth and Martian surface environments. Full article

A hydrochloric acid hydrometallurgical process was evaluated for Ni and Co extraction from a low-grade saprolitic laterite. The main characteristics of the process were (i) the application of a counter-current mode of operation as the main leaching step (CCL), and (ii) the treatment of pregnant leach solution (PLS) with a series of simple precipitation steps. It was found that, during CCL, co-dissolution of Fe was maintained at very low levels, i.e., about 0.6%, which improved the effectiveness of the subsequent PLS purification step. The treatment of PLS involved an initial precipitation step for the removal of trivalent metals, Fe, Al, and Cr, using Mg(OH)₂. The process steps that followed aimed at separating Ni and Co from Mn and the alkaline earths Mg and Ca, by a combination of repetitive oxidative precipitation and dissolution steps. Magnesium and calcium remained in the aqueous phase, Mn was removed as a solid residue of Mn(III)–Mn(IV) oxides, while Ni and Co were recovered as a separate aqueous stream. It was found that the overall Ni and Co recoveries were 40% and 38%, respectively. About 45% of Ni and 37% of Co remained in the leach residue, while 15% Ni and 20% Co were lost in the Mn oxides. Full article

This paper examines the effect of the aggregate type on concrete strength, and more specifically, how the petrographic characteristics of various aggregate rocks as well as their physico-mechanical properties influences the durability of C 25/30 strength class concrete. The studied aggregate rocks were derived from Veria-Naousa and Edessa ophiolitic complexes as well as granodiorite and albitite rocks from their surrounding areas in central Macedonia (Greece). Concretes were produced with constant volume proportions, workability, mixing and curing conditions using different sizes of each aggregate type. Aggregates were mixed both in dry and water saturated states in concretes. Six different types of aggregates were examined and classified in three district groups according to their physicomechanical properties, petrographic characteristics and surface texture. The classification in groups after the concrete compressive strength test verified the initial classification in the same three groups. Group I (ultramafic rocks) presented the lowest concrete strengths, depending on their high alteration degree and the low mechanical properties of ultramafic aggregates. Group II (mafic rocks and granodiorite) presented a wide range of concrete strengths, depending on different petrographic characteristics and mechanical properties. Group III (albite rocks) presented the highest concrete strengths, depending on their lowest alteration degree and their highest mechanical properties. Therefore, mineralogy and microstructure of the coarse aggregates affected the final strength of the concrete specimens. Full article

Karst bauxite deposits are currently investigated as a new resource for rare earth elements (REE) in order to avoid present and future supply shortfalls of these critical metals. The present work focuses on the geochemistry and mineralogy of the REE in karst bauxite deposits of the Catalan Coastal Range (CCR), NE-Spain. It is revealed that the studied bauxitic ores have a dominant breccia and local ooido-pisoidic and pelitomorphic texture. The bauxitic ores are mostly composed of kaolinite and hematite, as well as of lesser amounts of boehmite, diaspore, rutile and calcite. The mineralogy and major element composition indicate incomplete bauxitization of an argillaceous precursor material possibly derived from the erosion of the Mesozoic Ebro massif paleo-high. The studied bauxites are characterized by ∑REE (including Sc, Y) between 286 and 820 ppm (av. 483 ppm) and light REE to heavy REE (LREE/HREE) ratios up to 10.6. REE are mainly concentrated in phosphate minerals, identified as monazite-(Ce) and xenotime-(Y) of detrital origin and unidentified REE-phosphates of a possible authigenic origin. REE remobilization presumably took place under acidic conditions, whereas REE entrapment in the form of precipitation of authigenic rare earth minerals from percolating solutions was related to neutral to slightly alkaline conditions. During the bauxitization process no significant REE fractionation took place and the REE distribution pattern of the bauxitic ores was governed by the REE budget of the precursor material. Finally, adsorption as a main REE scavenging mechanism in the studied CCR bauxite deposits should not be considered, since the presented data did not reveal significant REE contents in Fe-and Mn-oxyhydroxides and clay minerals. Full article

A continuously growing demand for valuable non-ferrous metals and therefore an increase in their prices at the metal exchanges makes it necessary and profitable to investigate alternative metal resources. Polymetallic deep-sea nodules contain cobalt, copper, manganese, molybdenum and nickel, and are highly abundant on the sea floor. Developing a metallurgical process to recover the metal content from manganese nodules can close the predicted supply gap of critical metals like cobalt. This paper investigated a potential extraction process for valuable metals from manganese nodules supplied by the German Federal Institute for Geosciences and Natural Resources. The samples originated from the German license area of the Clarion-Clipperton Zone in the Pacific Ocean. Due to a low concentration of valuable metals in nodules, a pyrometallurgical enrichment step was carried out to separate cobalt, copper, molybdenum and nickel in a metallic phase. The manganese was discarded in the slag and recovered in a second smelting step as ferromanganese. To aid the experiments, FactSage^TM was used for thermodynamic modeling of the smelting steps. To increase metal yields and to alter the composition of the metal alloys, different fluxes were investigated. The final slag after two reduction steps were heavy-metal free and a utilization as a mineral product was desired to ensure a zero-waste process. Full article

Seismic reflection methods have been used for the exploration of mineral resources for several decades. However, despite their unmatched spatial resolution and depth penetration, they only have played a minor role in mineral discoveries so far. Instead, mining and exploration companies have traditionally focused more on the use of potential field, electric and electromagnetic methods. In this context, we present a case study of an underground Vertical Seismic Profiling (VSP) experiment, which was designed to image a (semi-)massive sulfide deposit located in the Kylylahti polymetallic mine in eastern Finland. For the measurement, we used a conventional VSP with three-component geophones and a novel fiber-optic Distributed Acoustic Sensing (DAS) system. Both systems were deployed in boreholes located nearby the target sulfide deposit, and used in combination with an active seismic source that was fired from within the underground tunnels. With this setup, we successfully recorded seismic reflections from the deposit and its nearby geological contrasts. The recording systems provided data with a good signal-to-noise ratio and high spatial resolution. In addition to the measurements, we generated a realistic synthetic dataset based on a detailed geological model derived from extensive drilling data and petrophysical laboratory analysis. Specific processing and imaging of the acquired and synthetic datasets yielded high-resolution reflectivity images. Joint analysis of these images and cross-validation with lithological logging data from 135 nearby boreholes led to successful interpretation of key geological contacts including the target sulfide mineralization. In conclusion, our experiment demonstrates the value of in-mine VSP measurements for detailed resource delineation in a complex geological setting. In particular, we emphasize the potential benefit of using fiber-optic DAS systems, which provide reflection data at sufficient quality with less logistical effort and a higher acquisition rate. This amounts to a lower total acquisition cost, which makes DAS a valuable tool for future mineral exploration activities. Full article

Ultrahigh-pressure (UHP) chromitites containing UHP minerals such as coesite and diamond have been reported from some ophiolites in Tibet and the Polar Urals. Their nature, i.e., origin, P-T path and abundance, however, are still controversial and left unclear. Here we describe chromitites in the Higashi-akaishi (HA) ultramafic complex in the Cretaceous Sanbagawa metamorphic belt, Japan, which experienced UHP condition (up to 3.8 GPa) at the peak metamorphism via subduction, in order to understand the nature of UHP chromitites. The HA peridotites typically contain garnets and are associated with eclogites, and their associated chromitites are expected to have experienced the UHP metamorphism. The Higashi-akaishi (HA) chromitites show banded to massive structures and are concordant to foliation of the surrounding peridotite. Chromian spinels in the chromitite and surrounding peridotites were sometimes fractured by deformation, and contain various inclusions, i.e., blade- and needle-like diopside lamellae, and minute inclusions of pyroxenes, olivine, and pargasite. The peculiar UHP minerals, such as coesite and diamond, have not been found under the microscope and the Raman spectrometer. Spinels in the HA chromitites show high Cr#s (0.7 to 0.85), and low Ti contents (<0.1 wt %), suggesting a genetic linkage to an arc magma. The HA chromitites share the basic petrographic and chemical features (i.e., diopside lamellae and arc-related spinel chemistry) with the UHP chromitites from Tibet and the Polar Urals. This suggests that some of the characteristics of the UHP chromitite can be obtained by compression, possibly via deep subduction, of low-P chromitite. Full article

This paper is the first description of natural copper-rich oxide spinels. They were found in deposits of oxidizing-type fumaroles related to the Tolbachik volcano, Kamchatka, Russia. This mineralization is represented by nine species with the following maximum contents of CuO (wt.%, given in parentheses): a new mineral thermaerogenite, ideally CuAl₂O₄ (26.9), cuprospinel, ideally CuFe³⁺₂O₄ (28.6), gahnite (21.4), magnesioferrite (14.7), spinel (10.9), magnesiochromite (9.0), franklinite (7.9), chromite (5.9), and zincochromite (4.8). Cuprospinel, formerly known only as a phase of anthropogenic origin, turned out to be the Cu-richest natural spinel-type oxide [sample with the composition (Cu_0.831Zn_0.100Mg_0.043Ni_0.022)_Σ0.996(Fe³⁺_1.725Al_0.219Mn³⁺_0.048Ti_0.008)_Σ2.000O₄ from Tolbachik]. Aluminum and Fe³⁺-dominant spinels (thermaerogenite, gahnite, spinel, cuprospinel, franklinite, and magnesioferrite) were deposited directly from hot gas as volcanic sublimates. The most probable temperature interval of their crystallization is 600–800 °C. They are associated with each other and with tenorite, hematite, orthoclase, fluorophlogopite, langbeinite, calciolangbeinite, aphthitalite, anhydrite, fluoborite, sylvite, halite, pseudobrookite, urusovite, johillerite, ericlaxmanite, tilasite, etc. Cu-bearing spinels are among the latest minerals of this assemblage: they occur in cavities and overgrow even alkaline sulfates. Cu-enriched varieties of chrome-spinels (magnesiochromite, chromite, and zincochromite) were likely formed in the course of the metasomatic replacement of a magmatic chrome-spinel in micro-xenoliths of ultrabasic rock under the influence of volcanic gases. The new mineral thermaerogenite, ideally CuAl₂O₄, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption. It forms octahedral crystals up to 0.02 mm typically combined in open-work clusters up to 1 mm across. Thermaerogenite is semitransparent to transparent, with a strong vitreous lustre. Its colour is brown, yellow-brown, red-brown, brown-yellow or brown-red. The mineral is brittle, with the conchoidal fracture, cleavage is none observed. D(calc.) is 4.87 g/cm³. The chemical composition of the holotype (wt.%, electron microprobe) is: CuO 25.01, ZnO 17.45, Al₂O₃ 39.43, Cr₂O₃ 0.27, Fe₂O₃ 17.96, total 100.12 wt.%. The empirical formula calculated on the basis of 4 O apfu is: (Cu_0.619Zn_0.422)_Σ1.041(Al_1.523Fe³⁺_0.443Cr_0.007)_Σ1.973O₄. The mineral is cubic, Fd-3m, a = 8.093(9) Å, V = 530.1(10) ų. Thermaerogenite forms a continuous isomorphous series with gahnite. The strongest lines of the powder X-ray diffraction pattern of thermaerogenite [d, Å (I, %) (hkl)] are: 2.873 (65) (220), 2.451 (100) (311), 2.033 (10) (400), 1.660 (16) (422), 1.565 (28) (511) and 1.438 (30) (440). Full article

Complex sulfides of thallium with As, Sb, or Bi and with other cations (‘thallium sulfosalts’) are a large group of crystal structures with extreme variability. Incorporation of the large Tl⁺ cation in them is solved in several different ways: housing of Tl in columns of capped trigonal coordination prisms, which form separate walls in the structure (in different combinations with Pb and/or Sb), regular alternation of large Tl with small cations (As), presence of structural arrays of Tl coordination polyhedra paralleled by arrays of As coordination pyramids with a frequency ratio 1:2, omission derivatives with cavities for Tl accommodation and formation of layer structures with thallium concentrated into separate (inter)layers of different types. The first principle leads to a large family of sartorite homologues and rare lillianite homologues, as well as to the chabournéite group. The second one to the hutchinsonite family, omission derivatives form the routhierite and galkhaite groups, and the 1:2 periodicity ratio principle results in several outstanding structures from different groups. Layer structures consist of two-component and three-component layer combinations. Close cation-cation interactions are present but rare. Full article

The Mersin ophiolite, Turkey, is of typical arc type based on geochemistry of crustal rocks without any signs of mid-ocean ridge (MOR) affinity. We examined its ultramafic rocks to reveal sub-arc mantle processes. Mantle peridotites, poor in clinopyroxene (<1.0 vol.%), show high Fo content of olivine (90–92) and Cr# [=Cr/(Cr + Al) atomic ratio] (=0.62–0.77) of chromian spinel. NiO content of olivine is occasionally high (up to 0.5 wt.%) in the harzburgite. Moho-transition zone (MTZ) dunite is also highly depleted, i.e., spinel is high Cr# (0.78–0.89), clinopyroxene is poor in HREE, and olivine is high Fo (up to 92), but relatively low in NiO (0.1–0.4 wt.%). The harzburgite is residue after high-degree mantle melting, possibly assisted by slab-derived fluid. The high-Ni character of olivine suggests secondary metasomatic formation of olivine-replacing orthopyroxene although replacement textures are unclear. The MTZ dunite is of replacive origin, resulted from interaction between Mg-rich melt released from harzburgite diapir and another harzburgite at the diapir roof. The MTZ dunite is the very place that produced the boninitic and replacive dunite. The MTZ is thicker (>1 km) in Mersin than in MOR-related ophiolite (mostly < 500 m), and this is one of the features of arc-type ophiolite. Full article

The Beiya Au deposit is the largest Cenozoic Au deposit in the Jinshajiang-Ailaoshan porphyry metallogenic belt. Numerous studies document that high water content and fO₂ are vital factors for the generation of Au mineralization. In this belt, only the Wandongshan and Hongnitang districts are considered to be of economic importance, while the other districts, such as Bailiancun, are barren. So in order to reveal the importance of water content and oxidation state for Beiya porphyry-style Au mineralization, the amphiboles and zircons compositions are used to evaluate the physicochemical conditions (e.g., pressure, temperature, fO₂, and water content) of the Wandongshan ore-fertile porphyries and Bailiancun ore-barren porphyries observed in the Beiya Au deposit. The results show that the water content of the Wandongshan parent magma (≤4.11 ± 0.4 wt %) are slightly higher than those of the parent magma at Bailiancun (≤3.91 ± 0.4 wt %), while the emplacement pressure of the Wandongshan parent magma (31.5–68.6 MPa) is much lower than that of the parent magma at Bailiancun (142.3–192.8 MPa), indicating that the Wandongshan magma reached water saturation earlier. In addition, the Wandongshan porphyries crystallized from more oxidized magma (average of ΔFMQ = +3.5) with an average temperature of 778 °C compared to the Bailiancun porphyries (average of ΔFMQ = +1.5) with a mean magmatic temperature of 770 °C. The Ce⁴⁺/Ce³⁺ ratio of zircon in the Wandongshan ore-related intrusions (average Ce⁴⁺/Ce³⁺ of 62.00) is much higher than that of the Bailiancun barren porphyries (average Ce⁴⁺/Ce³⁺of 23.15), which further confirmed Wandongshan ore-related magma is more oxidized than the Bailiancun barren magma. Therefore, melts that are more enriched in water and with a high oxidation state will be more fertile to form an economic porphyry-style Au system. Full article

The increasing release of potentially toxic metals from industrial processes can lead to highly elevated concentrations of these metals in soil, and ground- and surface-waters. Today, metal pollution is one of the most serious environmental problems and thus, the development of effective remediation strategies is of paramount importance. In this context, it is critical to understand how dissolved metals interact with mineral surfaces in soil–water environments. Here, we assessed the processes that govern the interactions between six common metals (Zn, Cd, Co, Ni, Cu, and Pb) with natural brucite (Mg(OH)₂) surfaces. Using atomic force microscopy and a flow-through cell, we followed the coupled process of brucite dissolution and subsequent nucleation and growth of various metal bearing precipitates at a nanometer scale. Scanning electron microscopy and Raman spectroscopy allowed for the identification of the precipitates as metal hydroxide phases. Our observations and thermodynamic calculations indicate that this coupled dissolution–precipitation process is governed by a fluid boundary layer at the brucite–water interface. Importantly, this layer differs in composition and pH from the bulk solution. These results contribute to an improved mechanistic understanding of sorption reactions at mineral surfaces that control the mobility and fate of toxic metals in the environment. Full article

Field portable X-ray fluorescence (pXRF) spectrometers are routinely used in mineral resources studies. To date, mineral resources studies have largely focussed on the application of pXRF to the exploration for deposits of base and precious metals. By contrast, studies using pXRF for the quantification of critical elements in geological materials are scarce since these elements are difficult to determine with energy-dispersive pXRF technology. This study explores the capability of pXRF spectrometers to detect and quantify critical elements (Ba, P, Nb, V, Co, REE, W, Bi, Hf, and Ta) in certified reference materials (CRMs). While precision of many critical elements is acceptable (<20% RSD), accuracy can be poor (>50% difference) when using pre-installed factory calibration software. Spectra collected during the pXRF measurements show that poor accuracy and false positives tend to be associated with spectral interferences. Distinct combinations of spectral interferences (line overlaps, Compton scattered peaks, and Si escape peaks) were observed in the different matrix types. Our results show that critical elements may be determined in common geological materials when pronounced peaks occur in the spectra and that matrix-match of standards and samples is essential. Hence, XRF spectra should be routinely reviewed to identify erroneous quantification due to spectral interferences. Full article

Following our recent work [Phys. Chem. Chem. Phys. 20:5190–99 (2018)] that provided the means to unambigously define and extract the three water regions at any charged interface (solid–liquid and air–liquid alike), denoted the BIL (Binding Interfacial Layer), DL (Diffuse Layer) and Bulk, and how to calculate their associated non-linear Sum Frequency Generation Spectroscopy (SFG) ${\chi }^2\left(\omega \right)$ spectroscopic contributions from Density Functional Theory (DFT)-based ab initio molecular dynamics simulations (DFT-MD/AIMD), we show here that the ${\chi }_{DL}^2\left(\omega \right)$ signal arising from the DL water region carries a wealth of essential information on the microscopic and macroscopic properties of interfaces. We show that the ${\chi }_{DL}^2\left(\omega \right)$ signal carries information on the surface potential and surface charge, the isoelectric point, EDL (Electric Double Layer) formation, and the relationship between a nominal electrolyte solution pH and surface hydroxylation state. This work is based on DFT-MD/AIMD simulations on a (0001) $\alpha$–quartz–water interface and on the air–water interface, with various surface quartz hydroxylation states and various electrolyte concentrations. The conclusions drawn make use of the interplay between experiments and simulations. Most of the properties listed above can now be extracted from experimental ${\chi }_{DL}^2\left(\omega \right)$ alone with the protocols given in this work, or by making use of the interplay between experiments and simulations, as described in this work. Full article

Over the last decade there has been an increasing interest in deep-sea mineral resources that may contribute to future raw metal supply. However, before seafloor massive sulfides (SMS) can be considered as a resource, alteration and weathering processes that may affect their metal tenor have to be fully understood. This knowledge cannot be obtained by assessing the surface exposures alone. Seafloor drilling is required to gain information about the third dimension. In 2016, three extinct seafloor massive sulfide mounds, located in the Trans-Atlantic Geotraverse (TAG) hydrothermal area of the Mid-Atlantic Ridge were drilled. A mineralogical and textural comparison of drill core and surface-grab samples revealed that in recent ceased mounds high-temperature copper assemblages typical for black smoker chimneys are still present whereas in longer extinct mounds the mineralogy is pre-dominated by an iron mineral assemblage. Zinc becomes remobilized early in the mound evolution and forms either a layer in the upper part of the mound or has been totally leached from its interior. Precipitation temperatures of sphalerite calculated using the Fe/Zn ratio can help to identify these remobilization processes. While the Fe/Zn ratios of primary sphalerites yield temperatures that are in very good agreement with fluid temperatures measured in white smokers, calculated temperatures for sphalerites affected by remobilization are too high for SMS. Overall drilling of SMS provides valuable information on the internal structure and mineralogy of the shallow sub-surface, however, additional drilling of SMS, at a greater depth, is required to fully understand the processes affecting SMS and their economic potential. Full article

A large amount of waste coming out from industries has posed a great challenge in its disposal and effect on the environment. Particularly fly ash, coming out from thermal power plants, which contains aluminosilicate minerals and creates a lot of environmental problems. In recent years, it has been found that geopolymer may give solutions to waste problems and environmental issues. Geopolymer is an inorganic polymer first introduced by Davidovits. Geopolymer concrete can be considered as an innovative and alternative material to traditional Portland cement concrete. Use of fly ash as a raw material minimizes the waste production of thermal power plants and protects the environment. Geopolymer concretes have high early strength and resistant to an aggressive atmosphere. Methods of preparation and characterization of fly ash-based geopolymers have been presented in this paper. The properties of geopolymer cement/mortar/concrete under different conditions have been highlighted. Fire resistance properties and 3D printing technology have also been discussed. Full article

Two Fe–Mn crusts among 35 samples, from six seamounts in the Canary Island Seamount Province, were selected as representatives of the endpoint members of two distinct types of genetic processes, i.e., mixed diagenetic/hydrogenetic and purely hydrogenetic. High-resolution analyses pursued the main aim of distinguishing the critical elements and their association with mineral phases and genetic processes forming a long-lived Fe–Mn crust. The Fe–Mn crust collected on the Tropic Seamount is composed of dense laminations of Fe-vernadite (>90%) and goethite group minerals, reflecting the predominance of the hydrogenetic process during their formation. Based on high-resolution age calculation, this purely hydrogenetic crust yielded an age of 99 Ma. The Fe–Mn crust collected on the Paps Seamount shows a typical botryoidal surface yielding an age of 30 Ma. electron probe microanalyzer (EPMA) spot analyses show two main types of manganese oxides, indicating their origin: (i) hydrogenetic Fe-vernadite, the main Mn oxide, and (ii) laminations of interlayered buserite and asbolane. Additionally, the occurrence of calcite, authigenic carbonate fluor-apatite (CFA) and palygorskite suggests early diagenesis and pervasive phosphatization events. Sequential leaching analysis indicated that Co, Ni, Cu, Ba and Ce are linked to Mn minerals. Therefore, Mn-oxides are enriched in Ni and Cu by diagenetic processes or in Co and Ce by hydrogenetic processes. On the other hand, Fe-oxides concentrate V, Zn, As and Pb. Moreover, the evidence of HREE enrichment related to Fe-hydroxides is confirmed in the mixed hydrogenetic/diagenetic crust. Full article

Silica polymorphs, such as quartz, tridymite, cristobalite, coesite, stishovite, seifertite, baddeleyite-type SiO₂, high-pressure silica glass, moganite, and opal, have been found in lunar and/or martian rocks by macro-microanalyses of the samples and remote-sensing observations on the celestial bodies. Because each silica polymorph is stable or metastable at different pressure and temperature conditions, its appearance is variable depending on the occurrence of the lunar and martian rocks. In other words, types of silica polymorphs provide valuable information on the igneous process (e.g., crystallization temperature and cooling rate), shock metamorphism (e.g., shock pressure and temperature), and hydrothermal fluid activity (e.g., pH and water content), implying their importance in planetary science. Therefore, this article focused on reviewing and summarizing the representative and important investigations of lunar and martian silica from the viewpoints of its discovery from lunar and martian materials, the formation processes, the implications for planetary science, and the future prospects in the field of “micro-mineralogy”. Full article

The new mineral species fiemmeite, Cu₂(C₂O₄)(OH)₂∙2H₂O, was found NE of the Passo di San Lugano, Val di Fiemme, Carano, Trento, Italy (latitude 46.312° N, longitude 11.406° E). It occurs in coalified woods at the base of the Val Gardena Sandstone (upper Permian) which were permeated by mineralizing solutions containing Cu, U, As, Pb and Zn. The oxalate anions have originated from diagenesis of the plant remains included in sandstones. The mineral forms aggregate up to 1 mm across of sky blue platelets with single crystals reaching maximum dimensions of about 50 μm. Associated minerals are: baryte, olivenite, middlebackite, moolooite, brochantite, cuprite, devilline, malachite, azurite, zeunerite/metazeunerite, tennantite, chalcocite, galena. Fiemmeite is monoclinic, space group: P2₁/c with a = 3.4245(6), b = 10.141(2), c = 19.397(3) Å, β = 90.71(1)°, V = 673.6(2) ų, Z = 4. The calculated density is 2.802 g/cm³ while the observed density is 2.78(1) g/cm³. The six strongest reflections in the X-ray powder diffraction pattern are: [d_obs in Å (I)(hkl)] 5.079(100)(020), 3.072(58)(112), 9.71(55)(002), 4.501(50)(022), 7.02(28)(012), 2.686(25)(114). The crystal structure was refined from single-crystal data to a final R₁ = 0.0386 for 1942 observed reflections [I > 2σ(I)] with all the hydrogen atoms located from a Difference–Fourier map. The asymmetric unit contains two independent Cu²⁺ cations that display a distorted square-bipyramidal (4+2) coordination, one oxalate anion, two hydroxyl anions and two water molecules. The coordination polyhedra of the two copper atoms share common edges to form polymeric rows running along [100] with composition [Cu₂(C₂O₄)(OH)₂∙2H₂O]_n. These rows are held together by a well-established pattern of hydrogen bonds between the oxalate oxygens not involved in the coordination to copper, the hydrogen atoms of the water molecules and the hydroxyl anions. Full article

A series of Si-bearing MgAl₂O₄-spinels were synthesized at 1500–1650 °C and 3–6 GPa. These spinels had SiO₂ contents of up to ~1.03 wt % and showed a substitution mechanism of Si⁴⁺ + Mg²⁺ = 2Al³⁺. Unpolarized Raman spectra were collected from polished single grains, and displayed a set of well-defined Raman peaks at ~610, 823, 856 and 968 cm⁻¹ that had not been observed before. Aided by the Raman features of natural Si-free MgAl₂O₄-spinel, synthetic Si-free MgAl₂O₄-spinel, natural low quartz, synthetic coesite, synthetic stishovite and synthetic forsterite, we infer that these Raman peaks should belong to the SiO₄ groups. The relations between the Raman intensities and SiO₂ contents of the Si-bearing MgAl₂O₄-spinels suggest that under some P-T conditions, some Si must adopt the M-site. Unlike the SiO₄ groups with very intense Raman signals, the SiO₆ groups are largely Raman-inactive. We further found that the Si cations primarily appear on the T-site at P-T conditions ≤~3–4 GPa and 1500 °C, but attain a random distribution between the T-site and M-site at P-T conditions ≥~5–6 GPa and 1630–1650 °C. This Si-disordering process observed for the Si-bearing MgAl₂O₄-spinels suggests that similar Si-disordering might happen to the (Mg,Fe)₂SiO₄-spinels (ringwoodite), the major phase in the lower part of the mantle transition zone of the Earth and the benchmark mineral for the very strong shock stage experienced by extraterrestrial materials. The likely consequences have been explored. Full article

One of the most promising strategies for the safe and permanent disposal of anthropogenic CO₂ is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO₂ capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO₃) carbonation (silicate dissolution → carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO_2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS. Full article

Following our previous works on dioctahedral clays, we extend the classical Polarizable Ion Model (PIM) to trioctahedral clays, by considering dry Na-, Cs-, Ca- and Sr-hectorites as well as hydrated Na-hectorite. The parameters of the force field are determined by optimizing the atomic forces and dipoles on density functional theory calculations. The simulation results are validated by comparison with experimental X-ray diffraction (XRD) data. The XRD patterns calculated from classical molecular dynamics simulations performed with the PIM force field are in very good agreement with experimental results. In the bihydrated state, the less structured electronic density profile obtained with PIM compared to the one from the state-of-the-art non-polarizable force field clayFF explains the slightly better agreement between the PIM results and experiments. Full article

In addition to iron and manganese, deep sea ferromanganese deposits, including nodules and crusts, contain significant amounts of economically interesting metals, such as cobalt (Co), nickel (Ni), copper (Cu), and rare Earth elements and yttrium (REY). Some of these metals are essential in the development of emerging and new-generation green technologies. However, the resource potential of these deposits is variable, and likely related to environmental conditions that prevail as they form. To better assess the environmental controls on the resource potential of ferromanganese deposits, we have undertaken a detailed study of the chemical composition of ferromanganese nodules and one crust sample from different oceanic regions. Textural and chemical characteristics of nodules from the North Atlantic and a crust from the South Pacific suggest that they acquire metals from a hydrogenous source. These deposits are potentially an economically important source of Co and the REY. On the other hand, nodules from the Pacific Ocean represent a marginal resource of these metals, due to their relatively fast growth rate caused by diagenetic precipitation. By contrast, they have relatively high concentrations of Ni and Cu. A nodule from the Arctic Ocean is characterised by the presence of significant quantities of detrital silicate material, which significantly reduces their metal resource. Full article

The interactions between additives and mineral precursors and intermediates are at the heart of additive-controlled crystallisation, which is of high importance for various fields. In this commentary, we reflect on potential modes of additive control according to classical nucleation theory on one hand, and from the viewpoint of the so-called pre-nucleation cluster pathway on the other. This includes a brief review of the corresponding literature. While the roles of additives are discussed generally, i.e., without specific chemical or structural details, corresponding properties are outlined where possible. Altogether, our discussion illustrates that “non-classical” nucleation pathways promise an improved understanding of additive-controlled scenarios, which could be utilised in targeted applications in various fields, ranging from scale inhibition to materials chemistry. Full article

The quartz-K-feldspar-cemented breccia of Berglia-Glassberget in the Lierne municipality in central Norway forms an ellipsoid structure 250 m × 500 m in size. The hydrothermal breccia is barren in terms of economic commodities but famous among mineral collectors for being a large and rich site of crystal quartz of various colours and habits. Despite being a famous collector site, the mineralization is rather unique in respect to its geological setting. It occurs within Late Palaeoproterozoic metarhyolites of the Lower Allochthon of the Norwegian Caledonides regionally isolated from any other contemporaneous hydrothermal or magmatic event. In order to understand better the formation of the Berglia-Glassberget breccia, the chemistry, fluid inclusion petrography and age of the breccia cement were determined. Structural features indicate that the Berglia-Glassberget is a fault-related, fluid-assisted, hydraulic breccia which formed by single pulse stress released by a seismic event. ⁴⁰Ar-³⁹Ar dating of K-feldspar cement revealed a middle Triassic age (240.3 ± 0.4 Ma) for this event. The influx into the fault zone of an aqueous CO₂-bearing fluid triggered the sudden fault movement. The high percentage of open space in the breccia fractures with cavities up 3 m × 3 m × 4 m in size, fluid inclusion microthermometry, and trace element chemistry of quartz suggests that the breccia was formed at depths between 4 and 0.5 km (1.1 to 0.1 kbar). The origin of the breccia-cementing, CO₂-bearing Na-HCO₃-SO₄ fluid may have been predominantly of metamorphic origin due to decarbonation reactions (T > 200 °C) of limestones of the underlying Olden Nappe. The decarbonation reactions were initiated by deeply derived, hot fluids channelled to sub-surface levels by a major fault zone, implying that the breccia is situated on a deep-seated structure. Regionally, the Berglia-Glassberget occurs at a supposed triple junction of long-lived fault zones belonging to the Møre-Trøndelag, Lærdal-Gjende and the Kollstraumen fault complexes. These fault systems and the associated Berglia-Glassberget earthquake are the expression of rifting and faulting in northern Europe during the middle/late Triassic. Full article

Ariegilatite, BaCa₁₂(SiO₄)₄(PO₄)₂F₂O (R $\overline{3}$ m, a = 7.1551(6) Å, c = 41.303(3) Å, V = 1831.2(3) ų, Z = 3), is a new member of the nabimusaite group exhibiting a modular intercalated antiperovskite structure derived from hatrurite. It was found in a few outcrops of pyrometamorphic rocks of the Hatrurim Complex located in the territories of Israel, Palestine and Jordan. The holotype specimen is an altered spurrite marble from the Negev Desert near Arad city, Israel. Ariegilatite is associated with spurrite, calcite, brownmillerite, shulamitite, CO₃-bearing fluorapatite, fluormayenite-fluorkyuygenite and a potentially new mineral, Ba₂Ca₁₈(SiO₄)₆(PO₄)₃(CO₃)F₃O. Ariegilatite is overgrown and partially replaced by stracherite, BaCa₆(SiO₄)₂[(PO₄)(CO₃)]F. The mineral forms flat disc-shaped crystals up to 0.5 mm in size. It is colorless, transparent, with white steaks and vitreous luster. Optically, ariegilatite is uniaxial, negative: ω = 1.650(2), ε = 1.647(2) (λ = 589 nm). The mean composition of the holotype ariegilatite, (Ba_0.98K_0.01Na_0.01)_Σ1(Ca_11.77Na_0.08Fe²⁺_0.06Mn²⁺_0.05Mg_0.04)_Σ12(Si_3.95Al_0.03Ti_0.02)_Σ4(P_1.70C_0.16Si_0.10S⁶⁺_0.03V_0.01)_Σ2F_2.04O_0.96, is close to the end-member formula. The structure of ariegilatite is described as a stacking of the two modules {F₂OCa₁₂(SiO₄)₄}⁴⁺ and {Ba(PO₄)₂}⁴⁻ along (001). Ariegilatite, as well as associated stracherite, are high-temperature alteration products of minerals of an early clinker-like association. These alterations took place under the influence of pyrometamorphism by-products, such as gases and fluids generated by closely-spaced combustion foci. Full article

Germanium, gallium and indium are in high demand due to their growing usage in high-tech and green-tech applications. However, the mineralogy and the mechanisms of concentration of these critical elements in different types of hydrothermal ore deposits remain poorly constrained. We investigated the mineralogical distribution of Ge, Ga and In at the Mt Carlton high-sulfidation epithermal deposit in NE Australia, using electron probe microanalysis and laser ablation inductively-coupled plasma mass spectrometry. Parageneses from which selected minerals were analyzed include: Stage 1 acid sulfate alteration (alunite), Stage 2A high-sulfidation enargite mineralization (enargite, argyrodite, sphalerite, pyrite, barite), Stage 2B intermediate-sulfidation sphalerite mineralization (sphalerite, pyrite, galena) and Stage 3 hydrothermal void fill (dickite). Moderate to locally high concentrations of Ga were measured in Stage 1 alunite (up to 339 ppm) and in Stage 3 dickite (up to 150 ppm). The Stage 2A ores show enrichment in Ge, which is primarily associated with argyrodite (up to 6.95 wt % Ge) and Ge-bearing enargite (up to 2189 ppm Ge). Co-existing sphalerite has comparatively low Ge content (up to 143 ppm), while Ga (up to 1181 ppm) and In (up to 571 ppm) are higher. Sphalerite in Stage 2B contains up to 611 ppm Ge, 2829 ppm Ga and 2169 ppm In, and locally exhibits fine colloform bands of an uncharacterized Zn-In mineral with compositions close to CuZn₂(In,Ga)S₄. Barite, pyrite and galena which occur in association with Stage 2 mineralization were found to play negligible roles as carriers of Ge, Ga and In at Mt Carlton. Analyzed reference samples of enargite from seven similar deposits worldwide have average Ge concentrations ranging from 12 to 717 ppm (maximum 2679 ppm). The deposits from which samples showed high enrichment in critical elements in this study are all hosted in stratigraphic sequences that locally contain carbonaceous sedimentary rocks. In addition to magmatic-hydrothermal processes, such rocks could potentially be important for the concentration of critical elements in high-sulfidation epithermal deposits. Full article

Quartz samples of different origin from 10 localities in the Southern Ural region, Russia have been investigated to characterize their trace element compositions and defect structures. The analytical combination of cathodoluminescence (CL) microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by inductively coupled plasma mass spectrometry (ICP-MS) revealed that almost all investigated quartz samples showed very low concentrations of trace elements (cumulative concentrations of <50 ppm with <30 ppm Al and <10 ppm Ti) and low abundances of paramagnetic defects, defining them economically as “high-purity” quartz (HPQ) suitable for high-tech applications. EPR and CL data confirmed the low abundances of substitutional Ti and Fe, and showed Al to be the only significant trace element structurally bound in the investigated quartz samples. CL microscopy revealed a heterogeneous distribution of luminescence centres (i.e., luminescence active trace elements such as Al) as well as features of deformation and recrystallization. It is suggested that healing of defects due to deformation-related recrystallization and reorganization processes of the quartz lattice during retrograde metamorphism resulted in low concentrations of CL activator and other trace elements or vacancies, and thus are the main driving processes for the formation of HPQ deposits in the investigated area. Full article