Michaela Krejčí Kotlánová

The intensification of clinker production is one of the strategies for reducing energy consumption and CO2 emissions associated with cement manufacturing. This study explores the use of various mineralisers and fluxes, specifically lithium, copper, and sulphur, added to the raw meal for clinker burning. These components can originate from both traditional and alternative fuels and raw materials. The influence of these elements on clinker melt formation, phase composition, and microstructure was investigated in the laboratory. Raw meals prepared from common cement materials were doped with chemically pure compounds Li2CO3, CuO, and (NH4)2SO4 in graded amounts. The thermal processes of the raw meals were monitored using differential thermal analysis coupled with a thermogravimetric analysis. The phase composition and microstructure of the resulting clinkers were analysed using X-ray powder diffraction and light microscopy. All dopants were found to lower the melt formation temperature, with lithium having the most significant effect. The dopants also caused changes in the phase composition and microstructure of the clinker, particularly affecting the size and shape of the alite crystals and the volume of the belite unit cell.

Mineralogy and formation conditions were studied in a newly found vein wolframite mineralization, cutting migmatitized paragneisses in the exocontact of a small Carboniferous granite body in the Pohled quarry, Moldanubian Zone of the Bohemian Massif, Czech Republic. The early stage of the rich mineral assemblage (36 mineral species) involves wolframite, columbite-group minerals, molybdenite, and scheelite hosted by quartz–muscovite–chlorite gangue, which was followed by base-metal sulfides in a quartz gangue, whereas the last stage included calcite gangue with fluorite and minor sulfides. The mineral assemblage points to the mobility of usually hardly soluble elements, including W, Sn, Zr, Nb, Th, Ti, Sc, Y, and REEs. A fluid inclusion study indicates a significant decrease in homogenization temperatures from 350–370 °C to less than 100 °C during vein formation. Fluids were aqueous, with a low salinity (0–12 wt. % NaCl eq.) and traces of CO₂, N₂, CH₄, H₂, and C₂H₆. The δ¹⁸O values of the fluids giving rise to quartz and scheelite are positive (min. 4‰–6‰ V-SMOW). The Eh and pH of the fluid also changed during evolution of the vein. Both wolframite and columbite-group minerals are anomalously enriched in Mg. We suggest that the origin of this distinct mineralization was related to the mixing of Mo,W-bearing granite-derived magmatic fluids with external basinal waters derived from contemporaneous freshwater (but episodically evaporated) piedmont basins. The basinal waters infiltrated into the subsurface along fractures formed in the extensional tectonic regime, and their circulation continued even after the ending of the activity of magmatic fluids. The studied wolframite mineralization represents the most complete record of the ‘hydrothermal’ history of a site adjacent to a cooling granite body in the study area. Moreover, there are broad similarities in the mineral assemblages, textures, and chemical compositions of individual minerals from other occurrences of wolframite mineralization around the Central Moldanubian Plutonic Complex, pointing to the genetic similarities of the Variscan wolframite-bearing veins in this area.

The Sn-W ore deposits in the Krupka surroundings are associated with greisens, which occur in the upper parts of Late Variscan granitoid intrusions. Fluid inclusions were studied in samples of quartz, cassiterite, apatite, fluorite, and topaz in greisenized granites, greisens, and hydrothermal veins with Sn-W mineralization. The greisenization process took place at temperatures 370–490 °C and pressures 155–371 bars, and associated fluids had predominantly low salinity and a low gas (CO₂, N₂ and CH₄) content. The post-greisenization stage was connected with the formation of (i) low-salinity (0–8 wt. % NaCl eq.) fluid inclusions with homogenization temperatures 35 wt. % NaCl eq.) fluid inclusions with homogenization temperatures 140–370 °C, often containing trapped crystals of quartz, topaz, and sulfides, or daughter crystals of salts and carbonates, which were identified by microthermometric measurements, electron microprobe analysis, and Raman spectroscopy. Analyses of fluid inclusion leachates have shown that Na and Ca chlorides predominate in fluids. According to hydrogen stable isotopes, the source of greisenizing and post-greisenizing fluids was not only magmatogenic but also meteoric water or fluids derived from sedimentary rocks.

An in situ electron microprobe study of detrital minerals yielded important insights into the diagenetic history of the Cretaceous-to-Paleogene flysch sandstones from the Chvalčov site, Rača Unit, Flysch Belt of the Outer Western Carpathians. Detrital titanite and a Fe-Ti mineral (probably ilmenite) were almost completely altered to TiO₂ minerals, which also newly crystallized in intergranular spaces of sandstone. Brookite, anatase, and, exceptionally, rutile were identified by Raman spectroscopy. Authigenic TiO₂ phases show complex composition with occasionally elevated contents of Fe, Nb, Zr, V, Sc, Cr, Al, Y, and/or P, which were likely sourced from altered neighboring heavy minerals. In addition, rare authigenic LREE- and Y-enriched apatite rims were observed on detrital apatite. The remobilization of REE, Y, and HFSE was likely mediated by acidic early diagenetic fluids enriched in fluoride and sulfate anions. The superimposed formation of calcite cement was associated with the dissolution of detrital garnet, feldspars, and quartz. The compositions of detrital apatite and garnet (Alm_60-82Prp_4-30Sps_0-24Grs_0-19) are comparable with those from adjacent parts of the Flysch Belt. Detrital rutile is enriched in Nb, V, Cr, and Zr. Our study illustrates the intensity of diagenetic alteration of detrital minerals in flysch sandstones as well as the usefulness of in-situ electron-microprobe investigations for the recognition of processes influencing heavy minerals in diagenetically altered sediments.

The mineralizing effect of CuO on microstructure and phase composition of SO₃ doped clinker was studied by a combination of phase analysis, light and scanning electron microscopy and QXRD. Results show proportionally higher C₄AF content in clinker interstitial matter due to CuO doping. CuO also lowers the SO₃ incorporation in main clinker phases C₃S and C₂S. Observation in back-scattered electrons revealed that Cu crystallizes mainly as a Cu-rich phase in the clinker interstitial matter and inclusions in crystals of C₂S with distorted structure. CuO partially inhibits the incorporation of Fe₂O₃ in C₂S. This article is protected by copyright. All rights reserved

Origin and chemical composition of fluids of hydrothermal ore veins at historical deposit Zlatý důl near Hlubočky (Lower Carboniferous of the Nízký Jeseník Upland) were studied using petrography, microthermometry and crush-leach analysis of fluid inclusions and analysis of stable isotopes of oxygen and carbon in carbonates, oxygen in quartz and sulphur in sulphides. Studied mineralization has epithermal and partly mesothermal character (Th = < 50 to 293 °C). The H2O-NaCl-CaCl2 system is mostly enclosed in the primary fluid inclusions in minerals of post-Variscan ore veins. These fluids had low to medium homogenization temperatures (68 to 293 °C) and moderate to high salinities (19–27 wt. % NaCl eq.). In contrast, low to moderate salinity (0–10 wt. % NaCl eq.) fluids of the system H2O-NaCl-KCl-(MgCl2-FeCl2) with low homogenization temperatures (< 50 to 110 °C) were enclosed in secondary fluid inclusions. The main source of water was probably evaporated seawater for older fluids. The source of carbon was in carbon of the homogenized Earth’s crust and partly in carbon of organic matter. Meteoric water is the main source for younger fluids. Origin of sulphur of sulphides is in the surrounding Lower Carboniferous sediments (shales). The high content of SO4 in fluids hosted by Fe-rich dolomite suggests the origin of the fluids in the evaporated Permian basins. Studied older quartz-galena vein is probably Variscan in age. Genetically similar mineralization can be found also at other localities in the Moravo-Silesian Lower Carboniferous (Culm, siliciclastics of the Lower Carboniferous age).