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Abatement of pharmaceutical pollutants from aquatic systems is crucial but remains a challenge. Semiconductor photocatalysis has emerged as an eco-friendly technique that utilizes renewable solar energy to address environmental issues. Naturally occurring and earth abundant hematite (Fe2O3) ores can be incorporated as a suitable component of a photocatalyst. Herein, Brazilian hematite was partially phase transformed into heterophase (consisting of α/γ-Fe2O3) by a simple single-stage heat treatment procedure. The method of synthesis was simple and economical, requiring neither solvents nor concentrated acids. The existence of α/γ-phases in the produced Fe2O3 (FO) was confirmed by X-ray diffraction analysis. After the phase transformation process, the local structure surrounding the Fe atoms was varied as evidenced from X-ray absorption spectroscopy. Given its low toxicity, narrow bandgap, and chemical stability, FO was further combined with g-C3N4 (CN) to form composites. The optical properties of the synthesized CNFO composites confirmed that the visible light harvesting ability of CN was enhanced after combining with FO. The CN sheets were grown uniformly over the surface of FO as evidenced from scanning electron microscopy. The prepared composites could degrade an aqueous solution of ofloxacin (OFX, 10 ppm) under visible light with remarkable efficacy. The performance of CNFO-5% was 4.8 times higher when compared to pure CN. The initial rate constant value for the photocatalytic degradation of OFX by CNFO-5% was 0.1271 min−1. The catalyst was stable even after five repeated cycles of photodegradation. The photoluminescence spectra and electrochemical measurements confirmed the efficient separation and transfer of the photogenerated charges across their interface. The investigations on different scavengers demonstrated that superoxide anion radicals and holes played a significant role in the degradation of OFX. The mechanism for the charge transfer was proposed to be a Z-scheme heterojunction. These results point to the potential of using inexpensive, abundant, and recyclable natural hematite ores as state-of-the-art photocatalysts for the elimination of pharmaceuticals in wastewater.

The general features of several important mineral deposits of polymetallic character in the Republic of Northern Macedonia that have been actively exploited in the past are described. These include the Buchim copper mine and Sasa, Zletovo and Toranica lead-zinc mines, as well as some ore prospects that have been extensively explored for years. In addition, sites with known ore reserves, but which are not yet at the exploitation stage are presented, including Plavica, Ilovica, Kadiica, Borov Dol and others. The elaborated RIS-RESERVES program is used to affirm numerous parameters related to the definition of ore reserves in the deposits, and has now provided the opportunity for preparation of an overview which shows the major metallogenetic characteristics of the deposits with their techno-economic parameters. This approach enables affirmation of the potential of the polymetallic ore deposits in the Republic of Northern Macedonia.

This paper is concerned with sublimates sampled in 2013–2020 in the near-crater zone and on the slopes of Alaid Volcano situated in the Kuril island arc. It was found that the near-crater zone contains native metals confined to zones of acidic leaching where the original lavas and tuffs have been transformed into opal-like rocks or rocks that are sharply enriched in hydroxides of trivalent iron. These zones were found to contain native gold, palladium, silver, chrome, copper, zinc and alloys of gold and palladium, copper and zinc, copper and tungsten. The mineral nomenclature in sublimates on the Alaid slopes is broader, while the temperature of their generation is lower. The ore minerals are dominated by copper-containing ones, and sublimates have been found with vanadium-containing minerals that belong to water-containing oxides and to silicates of vanadium. We have identified two genetic types of slope sublimates: (1) minerals that have crystallized from hydrothermal or vapor-hydrothermal solutions near vents of near-surface fumaroles and (2) copper and ferrous colloform formations that were generated by settling from colloidal solutions in shallow water of drying reservoirs, including small and large pools.

Many studies have proved the usefulness of Li-mica and chlorite geochemistry as indicators of the chemical and thermal evolution of magmatic systems. This study highlights the suitability of Li-micas as tracers of hydrothermal mineralizing events in world-class W-Sn deposits associated with Jurassic (190-150 Ma) granites in China through the complex magmatic-hydrothermal evolution of the Piaotang deposit (South Jiangxi). A paragenetic sequence has been established for the Piaotang deposit comprising (1) a first \"silicate-oxide\" stage that hosts abundant W-Sn mineralization (wolframite and cassiterite), (2) a \"calcic\" stage with scheelite and wolframite, (3) a \"base metal sulfides\" stage with cassiterite and wolframite, and (4) a late \"sulfide\" stage, involving for the first time a polyphase emplacement of the mineralization. Li-micas from the underlying granite, greisen, and the different stages represented in the veins, were studied. The chemistry of the micas (characterized by intermediate compositions between phlogopite-zinnwaldite-muscovite poles) demonstrates the presence of end-members representing three different fluids that were involved in the emplacement of the Piaotang deposit. These end-members can be linked to previous fluid inclusion studies conducted on this deposit. The three fluids are identified to be magmatic, meteoric (as previously reported in the literature), and also metamorphic, and are shown to have mixed throughout the different stages. Moreover, it appears that the magmatic fluids could not have been derived from the Piaotang biotite granite but instead must have originated from a more evolved rare metal granite that is presently unidentified. These fluids were responsible for the greisenization. Finally, chlorite geochemistry reveals the occurrence of a heating process (from 200°C in stage II to 300°C in stage III) during the post-mineralizing stages, which was responsible for the precipitation of new generations of ore-bearing minerals (cassiterite and wolframite) concomitant with a continuous gain of metals during the emplacement of the Piaotang deposit.

The new mineral theuerdankite, ideally Ag3AsO4, was found in the Alter Theuerdank Mine, Beerberg, St. Andreasberg, Goslar District, Lower Saxony, Germany. Theuerdankite occurs as aggregates of anhedral grains up to 3 mm in size, growing in cavities of strongly supergene-weathered material consisting of native silver and chlorargyrite (but with calcite present). It is dark violet, changing to reddish and black when exposed to the air and light. It has a grey to violet grey streak; when readily fresh, its streak is brownish-red. The Mohs hardness is ∼2. It is brittle with no observable cleavage or parting and with a conchoidal fracture. The calculated density is 6.620 g·cm-3. In reflected light, theuerdankite is dark grey with a pinkish tint, with no observable bireflectance, pleochroism, or anisotropy. It shows dark red internal reflections. The reflectance values for wavelengths recommended by the Commission on Ore Mineralogy of the International Mineralogical Association are (R, %): 13.3 (470 nm), 12.8 (546 nm), 12.7 (589 nm) and 12.5 (650 nm). The empirical formula (based on 4 apfu) is Ag3.00As1.00O4. Theuerdankite is cubic, space group P4̄3n, a = 6.144(2) Å, V = 231.93(13) Å3 and Z = 2. The six strongest powder X-ray diffraction lines are [dobs in Å, (I) hkl]: 3.0736, (22) 200; 2.7502, (100) 210; 2.5106, (55) 211; 1.7050, (36) 320; 1.6249, (44) 321; and 1.3412, (17) 421. The crystal structure of theuerdankite (R1 = 1.69% for 519 reflections having I > 3σ(I)), is isotypic to those of synthetic Ag3AsO4 and Ag3PO4. The Gram-Charlier development describing the higher-order tensors representing the atomic displacement parameters of the silver atom was implemented, documenting that silver tends to behave anharmonically in the theuerdankite structure at room temperature.

The Paleoproterozoic Stollberg Zn-Pb-Ag plus magnetite ore field contains SVALS-type stratabound, limestone-skarn hosted sulphide deposits within volcanic (bimodal felsic and mafic rocks)/volcaniclastic rocks metamorphosed to the amphibolite facies. The sulphide ores consist of semi-massive to disseminated to vein-network sphalerite-galena and pyrrhotite (with subordinate pyrite, chalcopyrite, arsenopyrite and magnetite). Thermochemical considerations and stabilities of minerals in the systems K-Al-Si-O-H and Fe-S-O and sulphur isotope values for sulphides of δ34SVCDT = +1.12 to +5.71 ‰ suggest that sulphur most likely formed by inorganic reduction of seawater sulphate that was carried in hydrothermally modified seawater fluid under the following approximate physicochemical conditions: T = 250o–350 oC, δ34SΣS = +3 ‰, I = ∼1 m NaCl and a total dissolved S content of ∼0.01 to 0.1 moles/kg H2O. However, a magmatic contribution of sulphur cannot be discounted. Carbon and oxygen isotope compositions of calcite in altered rocks spatially associated with mineralisation show values of δ13CVPDB = −2.3 to −0.8 ‰ and δ18OVSMOW = +9.5 to +11.2 ‰, with one anomalous sample exhibiting values of δ13CVPDB = −0.1 ‰ and δ18OVSMOW = +10.9 ‰. Most carbonates in ore show lighter C and O isotope values than those of Proterozoic (Orosirian) limestones and are likely the result of premetamorphic hydrothermal alteration involving modified seawater followed by decarbonation during regional metamorphism. The isotopically light C and O isotope values are consistent with those for carbonates spatially associated with other SVALS-type deposits in the Bergslagen ore district and suggest that such values may be used for exploration purposes.

The Fregeneda-Almendra pegmatite field of the Iberian Massif represents a typical expression of peraluminous rare-metal magmatism that occurred over western Europe at the end of the Variscan orogeny. It is the host for two main types of Li-mineralized intrusions, identified at the scale of the Variscan belt, including petalite- or spodumene-rich pegmatites, as well as Li-mica-rich pegmatites, for which the origin of mineralogical-chemical differences is not yet understood. Here, we provide cassiterite and columbite-group mineral (CGM) U-Pb ages along with oxide, mica and phosphate mineral compositions for Li-pegmatites from the Fregeneda-Almendra field in order to assess their petrogenesis and tectonic-magmatic context of emplacement. U-Pb geochronology indicates that petalite-rich and Li-mica-rich pegmatites were mostly emplaced sub-synchronously from 315 ± 6 to 308 ± 6 Ma, during strike-slip deformation and granitic magmatism within an anatectic dome bounding the pegmatite field. U-Pb data and pegmatite geographic zonation suggest that Li-pegmatites were sourced from buried equivalents of leucogranites and migmatites from the dome. Li-pegmatites experienced a complex crystallization including K-feldspar, petalite, topaz, Nb-Ta-Fe-Mn-rich cassiterite, amblygonite-group minerals (AGM) and CGM as early magmatic phases, followed by lepidolite for Li-mica-rich pegmatites. At the magmatic-hydrothermal transition, notably leading to the formation of Nb-Ta-Mn-Fe-poor cassiterite hosting CGM inclusions, earlier minerals were resorbed by muscovite and albite. A later F-rich hydrothermalism is locally reflected by zinnwaldite overgrowths on muscovite. Cassiterite, CGM and micas from petalite-rich pegmatites show lower Mn/Fe ratios and higher Ti contents, along with lower Zr-Ga contents for cassiterite, than that from Li-mica-rich pegmatites. Such behavior is consistent with a magmatic differentiation process whereby Ti content decreased and the degree of Mn-Fe geochemical fractionation and solubilities of Ga and Zr increased in the melts, possibly in relation with high fluorine activity. In Li-mica-rich pegmatites, AGM equilibrated with a melt with up to 2 wt% F, similar to that in equilibrium with lepidolite (1-3 wt%). In petalite-rich pegmatites, the relatively high F concentration of the melts equilibrated with AGM (≤ 1.5 wt% F) contrasts with the liquid equilibrated with muscovite (#lt; 0.5 wt% F). This can be accounted for by muscovite crystallization after the exsolution of a F-rich aqueous phase at the magmatic-hydrothermal transition. Relatively similar F contents in the initial melts of petalite- and Li-mica-rich pegmatites support the hypothesis that the stability of lepidolite does not only involve high F but also a low H2O/F activity ratio. For the Fregeneda-Almendra Li-mica-rich pegmatites, this could be explained by a decrease of melt H2O solubility due to a relatively low pressure of emplacement.

Hakite-(Cd), hakite-(Fe) and hakite-(Zn) are new minerals belonging to the tetrahedrite group and forming, along with hakite-(Hg), the hakite series. They have been discovered in samples collected from the Bytíz deposit, in the uranium and base-metal Príbram ore district, Central Bohemia, Czech Republic. They occur as anhedral grains, up to 300 µm in size, in a calcite gangue, associated with clausthalite, cadmoselite, hakite-(Hg) [for hakite-(Cd)], berzelianite, bukovite, bytízite, crookesite, chaméanite, eskebornite, príbramite, the not yet approved giraudite-(Hg) and giraudite-(Cu), hakite-(Hg), umangite, chalcopyrite, tetrahedrite-(Zn) and a new Cu-As selenide [for hakite-(Fe) and -(Zn)]. The three new species are black, with a metallic lustre. Mohs hardness is ca. 3 1/2-4; calculated density is 6.019 (Hak-Cd), 6.011 (Hak-Fe) and 6.081 g·cm-3 (Hak-Zn). In reflected light, they are isotropic, pale grey with bluish (Hak-Cd) or brownish (Hak-Fe and Hak-Zn) shades. Empirical formulae of hakite-(Cd), hakite-(Fe), and hakite-(Zn) are Cu9.71Ag0.24Cd1.51Hg0.43Zn0.03(Sb3.94As0.13)Σ4.07Se11.35S1.5 7, Cu10.11Ag0.18Fe0.81Zn0.50Hg0.26(Sb3.72As0.41)Σ4.13Se12.65S0. 12, and Cu10.03Ag0.24Zn0.61Fe0.53Hg0.45(Sb3.55As0.60)Σ4.15Se12.82S0. 08, respectively. These formulae correspond to the end-member formulae Cu6(Cu4Cd2)Sb4Se13 (Hak-Cd), Cu6(Cu4Fe2)Sb4Se13 (Hak-Fe), and Cu6(Cu4Zn2)Sb4Se13 (Hak-Zn). All these new members of the hakite series are cubic, I4̄3m, Z = 2, with unit-cell parameters a = 10.8860(6) Å, V = 1290.0(2) Å3 (Hak-Cd); a = 10.7983(4) Å, V = 1259.12(14) Å3 (Hak-Fe); and a = 10.8116(14) Å, V = 1263.8(5) Å3 (Hak-Zn). These species are isotypic with the other members of the tetrahedrite group, and their crystal structures have been refined on the basis of single-crystal X-ray diffraction data down to R1 values of 0.0230 (Hak-Cd), 0.0254 (Hak-Fe), and 0.0302 (Hak-Zn). These structural data allow us to describe the S-to-Se partitioning in hakite-series minerals and to understand the mechanisms avoiding too short Me-Se distances in these selenides.

Okruginite, Cu2SnSe3 is a new mineral discovered from the high-sulfidation epithermal Au Ozernovskoye deposit, Kamchatka peninsula, Russia. It occurs as distinct Se-rich zones in Se-bearing mohite crystals or forms aggregates of small crystals 10-15 µm in size in quartz. In plane-polarised light, okruginite appears brownish grey. Pleochroism and bireflectance are discernible, anisotropy is weak, with rotation tints pale blue-grey to pale grey-brown; it exhibits no internal reflections. Reflectance values of the synthetic analogue of okruginite in air (R1, R2 in %) are: 25.9, 26.5 at 470 nm, 27.5, 26.5 at 546 nm, 27.8, 28.4 at 589 nm and 27.7, 28.4 at 650 nm. Twenty seven electron-microprobe analyses of okruginite give an average composition: Cu 29.48, Sn 28.10, Se 33.40 and S 8.75, total 99.73 wt.%, corresponding to the empirical formula Cu1.99Sn1.02(Se1.82S1.17)Σ2.99 based on 6 atoms; the average of seven analyses on its synthetic analogue is: Cu 23.62, Sn 24.37 and Se 49.09, total 97.08 wt.%, corresponding to Cu1.86Sn1.03Se3.11. The density, calculated on the basis of the empirical formula, is 5.126 g/cm3. The mineral is monoclinic, space group Cc, with a = 6.9906(2), b = 12.0712(4) Å, c = 6.9723(2) Å, β = 109.350(10)°, V = 555.1(2) Å3 and Z = 4. The crystal structure was solved and refined from the powder X-ray-diffraction data of synthetic Cu2SnSe3. Okruginite is the selenium-end member of the Cu2SnS3-Cu2SnSe3 solid solution. The mineral name is in honour of Dr. Victor Mikhailovich Okrugin, a Russian mineralogist, for his contributions to mineralogy and geology of epithermal deposits, in particular of the Au-Ag deposits in Kamchatka.

This work presents data for the mineral assemblages, composition and Raman spectroscopy of proximal secondary Be and associated minerals in pseudomorphs after beryl from granitic pegmatites located along the contacts of major regional geological units. The pegmatites differ in their position relative to the ductile to brittle shear zones within the Rozna-Olsi. ore field (U-deposit), Czech Republic. Extensive dissolution of beryl crystals in the beryl-columbite pegmatites Drahonin IV and Vezna I situated within or close to the shear zones is evident in contrast to minor alteration of beryl in the Dolni Rozinka and Kovarova pegmatites located outside of the shear zones. Near-total replacement of beryl crystals, up to 40 cm in length, from the Drahonin IV pegmatite, located in the Olsi shear zone formed the following secondary Be minerals in order of their abundance: bavenite-bohseite > bertrandite >> milarite > hydroxylgugiaite. This assemblage is also characterised by the presence of sulfides (pyrite, galena, sphalerite) and zeolites. Such an extensive replacement process required a substantial fluid flow and is very possibly related to the pre-uranium quartz-sulfide and carbonate-sulfide mineralisation events Rozna Olsi ore field. Alteration products resulting from breakdown of beryl Vezna I pegmatite follow the sequential substages (bertrandite + ± K-feldspar ± harmotone → epididymite + K-feldspar → hydroxylgugiaite + K-feldspar) and locally show cross-cutting textures. These assemblages were generated by post-magmatic residual fluids (early assemblage bertrandite + K-feldspar) as well as fluids related to a retrograde stage of metamorphism, compositionally contrasting with the host serpentinite, and perhaps also hydrothermal processes associated with the Olsi shear zone. The pegmatites Dolni Rozinka, located outside of the shear zones, exhibit only a low degree of alteration and have differing textural and paragenetic development. Highly variable assemblages of secondary minerals after beryl are excellent mineral indicators of hydrothermal overprinting in granitic pegmatites during a variety of subsolidus processes.