The subject of this work was supergene uranium mineralization and the YREE concentrations within.... more The subject of this work was supergene uranium mineralization and the YREE concentrations within. YREE differentiation patterns were used to recreate the prevailing crystallization conditions of abandoned mine dumps in Kromnów, Kopaniec, and Radoniów, located in the Izera Metamorphic Complex, Sudetes Mts. The collected samples were investigated using PXRD, SEM-EDS, and EPMA. YREE concentrations were measured using LA-ICP-MS. The secondary uranium mineralization from these locations consists of phosphates (meta-autunite, meta-torbernite, metauranocircite-I, saleéite, bassetite, phosphuranylite), arsenates (zeunerite), silicates (uranophane, sklodowskite), and uranyl hydroxides (likely becquerelite). Moreover, in Radoniów, phosphuranylite was found; it had not been found in Poland previously. Uranyl mineral assemblages indicate the diversity of chemistry of their mother solutions and suggest their weakly acidic character. The YREE content in secondary uranium minerals also reflects th...
As a result of external stress applied to crystals, ions relax, in addition to shortening the bon... more As a result of external stress applied to crystals, ions relax, in addition to shortening the bond lengths, by changing their shape and volume. Modern mineralogy is founded on spherical ions/atoms, i.e. the close packing of spheres, ionic/atomic radii, and Pauling and Goldschmidt rules. More advanced, quantum crystallography has led to detailed quantitative studies of electron density in minerals. Here we innovatively apply it to high pressure studies up to 4.2 GPa of the mineral hsianghualite. With external stress, electron density redistributes inside ions and among them. For most ions, atomic volumes decrease; however, for silicon atomic volume increases. With growing pressure, we observed the higher contraction of cations in bonding directions, but a slighter expansion towards nonbonding directions. It is possible to trace the spatial redistribution of the electron density in ions even at the level of hundredths parts of an electron per cubic angstrom. This opens a new perspecti...
The Podgórze uranium deposit is located near Kowary in the Sudetes Mountains, SW Poland. The mine... more The Podgórze uranium deposit is located near Kowary in the Sudetes Mountains, SW Poland. The mine is located in the Karkonosze-Izera block, largely comprising Cambrian to Devonian metamorphic rocks intruded by the Variscan Karkonosze granite. Uranyl minerals from the Podgórze mine can be divided into three assemblages. The first one is associated with heavily ventilated mining galleries. The next assemblage is related to the outflow of water from fissures in the walls of the mine galleries. The last assemblage appears in the mine dump, where there is increased activity of other weathering products. The main purpose of this paper is to determine the mineralogical characteristics of uranyl minerals from the abandoned Podgórze uranium mine and reconstruct the physicochemical crystallization conditions based on the concentrations of rare earth elements (REEs) in these minerals. The results of thermodynamic modeling show that the aqueous species of uranyl ion in the mine water are repres...
The paper deals with the mode of occurrence and crystal morphology of fibroferrite, pickeringite ... more The paper deals with the mode of occurrence and crystal morphology of fibroferrite, pickeringite and slavikite from the oxidation zone of pyrite-bearing sericite-chlorite schists in Wieściszowice (Lower Silesia). It also presents the results of X-ray, thermal and chemical studies of these minerals. Monoclinic acicular fibroferrite and pick-eringite crystals as well as trigonal tabular slavikite ones, accompanied by copiapite, gypsum, alunogen and epsomite, form incrustations and efflorescences on the surface of weathering schists. Their crystallization from solutions rich in Fe 3+ , Al and Mg is associated with the decomposition of chlorite under the influence of solutions containing sulphuric acid derived from oxidation of pyrite. The above described sulphate minerals are not stable due to their high solubility in water. Therefore, definite atmospherical conditions are necessary for their crystallization and preservation. JAN PARAFINIUK FIBROFERRYT, SLAVIKIT I PICKERINGIT ZE STREFY...
Pressure is well known to dramatically alter physical properties and chemical behaviour of materi... more Pressure is well known to dramatically alter physical properties and chemical behaviour of materials, much of which is due to the changes in chemical bonding that accompany compression. Though it is relatively easy to comprehend this correlation in the discontinuous compression regime, where phase transformations take place, understanding of the more subtle continuous compression effects is a far greater challenge, requiring insight into the finest details of electron density redistribution. In this study, a detailed examination of quantitative electron density redistribution in the mineral langbeinite was conducted at high pressure. Langbeinite is a potassium magnesium sulfate mineral with the chemical formula [K2Mg2(SO4)3], and crystallizes in the isometric tetartoidal (cubic) system. The mineral is an ore of potassium, occurs in marine evaporite deposits in association with carnallite, halite and sylvite, and gives its name to the langbeinites, a family of substances with the sam...
College of Inter-Faculty Individual Studies in Mathematics and Natural Sciences 6 (MISMaP), Żwirk... more College of Inter-Faculty Individual Studies in Mathematics and Natural Sciences 6 (MISMaP), Żwirki and Wigury 93, 02-089 Warszawa, Poland 7 Biological and Chemical Research Centre, University of Warsaw, Żwirki i 8 Wigury 101, 02-089 Warszawa, Poland. 9 Institute of Mineralogy, Geochemistry and Petrology, University of Warsaw, 0210 089 Warszawa, Poland. 11 Diamond Light Source, Harwell Science and Innovation Campus, Didcot, 12 Oxfordshire OX11 0DE, UK. 13 Faculty of Natural & Environmental Sciences, School of Chemistry, University of 14 Southampton, Highfield, Southampton, SO17 1BJ, UK. 15 16 E-mail: kwozniak@chem.uw.edu.pl 17 18 19 ABSTRACT 20 21 The crystal structure of alumohydrocalcite was determined using 22 synchrotron X-ray radiation. Alumohydrocalcite crystallizes in the triclinic 1 23
Secondary gypsum is formed as a result of sulfur oxidation in the native . sulfur deposits of the... more Secondary gypsum is formed as a result of sulfur oxidation in the native . sulfur deposits of the Fore-Carpathian Depression, Southern Poland. Limestones containing native sulfur exposed to the activity of atmospheric weathering easily change into gypsum. The secondary gypsum occurs as fine, dispersed crystals, crusts and crystal groups growing on the surface of rocks, which are exposed for a longer period. The newly formed gypsum differs in the sulfur isotope composition from its older generations occurring in the deposits. The differentiation of isotopic composition of secondary gypsum in relation to native sulfur is much higher than it is indicated by the experimental data. There was recorded gypsum of both lighter and heavier isotopic composition than the native sulfur. The sulfur oxidation in the deposits can proceed either inorganically or by the sulfur bacteria. There was observed the secondary gypsum which crystallized from the formation waters collected in ephemeral pools i...
The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-h... more The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-heaps. Three burning heaps located in the Upper Silesian coal basin in Czerwionka-Leszczyny, Radlin and Rydułtowy near Rybnik were selected for the research. The occurrence of godovikovite, millosevichite, steklite and an unnamed MgSO4, sometimes accompanied by subordinate admixtures of mikasaite, sabieite, efremovite, langbeinite and aphthitalite has been recorded from these locations. Occasionally they form monomineral aggregates, but usually occur as mixtures practically impossible to separate. The minerals form microcrystalline masses with a characteristic vesicular structure resembling a solidified foam or pumice. The sulfates crystallize from hot fire gases, similar to high temperature volcanic exhalations. The gases transport volatile components from the center of the fire but their chemical compositions are not yet known. Their cooling in the near-surface part of the heap results ...
Parafiniuk J. and Kruszewski Ł. (2009) — Am mo nium min er als from burn ing coal-dumps of the Up... more Parafiniuk J. and Kruszewski Ł. (2009) — Am mo nium min er als from burn ing coal-dumps of the Up per Silesian Coal Ba sin (Po land).
As sem blages com posed of 11 am mo nium min er als, mainly sulphates and chlo rides, were re cor... more As sem blages com posed of 11 am mo nium min er als, mainly sulphates and chlo rides, were re corded from four burn ing coal-dumps (BCD) in the Up per Silesian Coal Ba sin. Most of them are newly re corded from Po land. Min er als were iden ti fied us ing PXRD and SEM with EDS anal y ses. Salammoniac, NH4Cl, and tschermigite, (NH4)Al(SO4)2·12H2O are the most com mon spe cies on the BCD stud ied. Kremersite, (NH4,K)2[FeCl5(H2O)], is rare and co ex ists with mem bers of the ammonioalunite–ammoniojarosite se ries. Boussingaultite, (NH4)2Mg(SO4)2·6H2O, and more rarely clairite, (NH4)2Fe3(SO4)4(OH)3·3H2O, and mascagnite, (NH4)2SO4, ac com pany nu mer ous Mg, Al, Fe and Ca sul phate min er als. These usu ally oc cur as very fine ad mix tures form ing coat ings, small nod ules or po rous masses and were found on the BCD sur face close to gas vents. Also a mas sive sul phate crust was found in the deeper part of the BCD nearby the fire zone. This crust is com posed mainly of an hy drous sul...
X-ray diffraction studies of crystals under pressure and quantitative experimental charge density... more X-ray diffraction studies of crystals under pressure and quantitative experimental charge density analysis are among the most demanding types of crystallographic research. A successful feasibility study of the electron density in the mineral grossular under 1 GPa pressure conducted at the CRISTAL beamline at the SOLEIL synchrotron is presented in this work. A single crystal was placed in a diamond anvil cell, but owing to its special design (wide opening angle), short synchrotron wavelength and the high symmetry of the crystal, data with high completeness and high resolution were collected. This allowed refinement of a full multipole model of experimental electron distribution. Results are consistent with the benchmark measurement conducted without a diamond-anvil cell and also with the literature describing investigations of similar structures. Results of theoretical calculations of electron density distribution on the basis of dynamic structure factors mimic experimental findings ...
Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials
On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using a... more On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using an Ag source at 90 K to a resolution of 1.63 Å−1, a quantitative experimental charge density distribution has been obtained for fluorite (CaF2). The atoms-in-molecules integrated experimental charges for Ca2+ and F− ions are +1.40 e and −0.70 e, respectively. The derived electron-density distribution, maximum electron-density paths, interaction lines and bond critical points along Ca2+...F− and F−...F− contacts revealed the character of these interactions. The Ca2+...F− interaction is clearly a closed shell and ionic in character. However, the F−...F− interaction has properties associated with the recently recognized type of interaction referred to as `charge-shift' bonding. This conclusion is supported by the topology of the electron localization function and analysis of the quantum theory of atoms in molecules and crystals topological parameters. The Ca2+...F− bonded radii – measure...
The subject of this work was supergene uranium mineralization and the YREE concentrations within.... more The subject of this work was supergene uranium mineralization and the YREE concentrations within. YREE differentiation patterns were used to recreate the prevailing crystallization conditions of abandoned mine dumps in Kromnów, Kopaniec, and Radoniów, located in the Izera Metamorphic Complex, Sudetes Mts. The collected samples were investigated using PXRD, SEM-EDS, and EPMA. YREE concentrations were measured using LA-ICP-MS. The secondary uranium mineralization from these locations consists of phosphates (meta-autunite, meta-torbernite, metauranocircite-I, saleéite, bassetite, phosphuranylite), arsenates (zeunerite), silicates (uranophane, sklodowskite), and uranyl hydroxides (likely becquerelite). Moreover, in Radoniów, phosphuranylite was found; it had not been found in Poland previously. Uranyl mineral assemblages indicate the diversity of chemistry of their mother solutions and suggest their weakly acidic character. The YREE content in secondary uranium minerals also reflects th...
As a result of external stress applied to crystals, ions relax, in addition to shortening the bon... more As a result of external stress applied to crystals, ions relax, in addition to shortening the bond lengths, by changing their shape and volume. Modern mineralogy is founded on spherical ions/atoms, i.e. the close packing of spheres, ionic/atomic radii, and Pauling and Goldschmidt rules. More advanced, quantum crystallography has led to detailed quantitative studies of electron density in minerals. Here we innovatively apply it to high pressure studies up to 4.2 GPa of the mineral hsianghualite. With external stress, electron density redistributes inside ions and among them. For most ions, atomic volumes decrease; however, for silicon atomic volume increases. With growing pressure, we observed the higher contraction of cations in bonding directions, but a slighter expansion towards nonbonding directions. It is possible to trace the spatial redistribution of the electron density in ions even at the level of hundredths parts of an electron per cubic angstrom. This opens a new perspecti...
The Podgórze uranium deposit is located near Kowary in the Sudetes Mountains, SW Poland. The mine... more The Podgórze uranium deposit is located near Kowary in the Sudetes Mountains, SW Poland. The mine is located in the Karkonosze-Izera block, largely comprising Cambrian to Devonian metamorphic rocks intruded by the Variscan Karkonosze granite. Uranyl minerals from the Podgórze mine can be divided into three assemblages. The first one is associated with heavily ventilated mining galleries. The next assemblage is related to the outflow of water from fissures in the walls of the mine galleries. The last assemblage appears in the mine dump, where there is increased activity of other weathering products. The main purpose of this paper is to determine the mineralogical characteristics of uranyl minerals from the abandoned Podgórze uranium mine and reconstruct the physicochemical crystallization conditions based on the concentrations of rare earth elements (REEs) in these minerals. The results of thermodynamic modeling show that the aqueous species of uranyl ion in the mine water are repres...
The paper deals with the mode of occurrence and crystal morphology of fibroferrite, pickeringite ... more The paper deals with the mode of occurrence and crystal morphology of fibroferrite, pickeringite and slavikite from the oxidation zone of pyrite-bearing sericite-chlorite schists in Wieściszowice (Lower Silesia). It also presents the results of X-ray, thermal and chemical studies of these minerals. Monoclinic acicular fibroferrite and pick-eringite crystals as well as trigonal tabular slavikite ones, accompanied by copiapite, gypsum, alunogen and epsomite, form incrustations and efflorescences on the surface of weathering schists. Their crystallization from solutions rich in Fe 3+ , Al and Mg is associated with the decomposition of chlorite under the influence of solutions containing sulphuric acid derived from oxidation of pyrite. The above described sulphate minerals are not stable due to their high solubility in water. Therefore, definite atmospherical conditions are necessary for their crystallization and preservation. JAN PARAFINIUK FIBROFERRYT, SLAVIKIT I PICKERINGIT ZE STREFY...
Pressure is well known to dramatically alter physical properties and chemical behaviour of materi... more Pressure is well known to dramatically alter physical properties and chemical behaviour of materials, much of which is due to the changes in chemical bonding that accompany compression. Though it is relatively easy to comprehend this correlation in the discontinuous compression regime, where phase transformations take place, understanding of the more subtle continuous compression effects is a far greater challenge, requiring insight into the finest details of electron density redistribution. In this study, a detailed examination of quantitative electron density redistribution in the mineral langbeinite was conducted at high pressure. Langbeinite is a potassium magnesium sulfate mineral with the chemical formula [K2Mg2(SO4)3], and crystallizes in the isometric tetartoidal (cubic) system. The mineral is an ore of potassium, occurs in marine evaporite deposits in association with carnallite, halite and sylvite, and gives its name to the langbeinites, a family of substances with the sam...
College of Inter-Faculty Individual Studies in Mathematics and Natural Sciences 6 (MISMaP), Żwirk... more College of Inter-Faculty Individual Studies in Mathematics and Natural Sciences 6 (MISMaP), Żwirki and Wigury 93, 02-089 Warszawa, Poland 7 Biological and Chemical Research Centre, University of Warsaw, Żwirki i 8 Wigury 101, 02-089 Warszawa, Poland. 9 Institute of Mineralogy, Geochemistry and Petrology, University of Warsaw, 0210 089 Warszawa, Poland. 11 Diamond Light Source, Harwell Science and Innovation Campus, Didcot, 12 Oxfordshire OX11 0DE, UK. 13 Faculty of Natural & Environmental Sciences, School of Chemistry, University of 14 Southampton, Highfield, Southampton, SO17 1BJ, UK. 15 16 E-mail: kwozniak@chem.uw.edu.pl 17 18 19 ABSTRACT 20 21 The crystal structure of alumohydrocalcite was determined using 22 synchrotron X-ray radiation. Alumohydrocalcite crystallizes in the triclinic 1 23
Secondary gypsum is formed as a result of sulfur oxidation in the native . sulfur deposits of the... more Secondary gypsum is formed as a result of sulfur oxidation in the native . sulfur deposits of the Fore-Carpathian Depression, Southern Poland. Limestones containing native sulfur exposed to the activity of atmospheric weathering easily change into gypsum. The secondary gypsum occurs as fine, dispersed crystals, crusts and crystal groups growing on the surface of rocks, which are exposed for a longer period. The newly formed gypsum differs in the sulfur isotope composition from its older generations occurring in the deposits. The differentiation of isotopic composition of secondary gypsum in relation to native sulfur is much higher than it is indicated by the experimental data. There was recorded gypsum of both lighter and heavier isotopic composition than the native sulfur. The sulfur oxidation in the deposits can proceed either inorganically or by the sulfur bacteria. There was observed the secondary gypsum which crystallized from the formation waters collected in ephemeral pools i...
The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-h... more The subject of this work is the assemblage of anhydrous sulfate minerals formed on burning coal-heaps. Three burning heaps located in the Upper Silesian coal basin in Czerwionka-Leszczyny, Radlin and Rydułtowy near Rybnik were selected for the research. The occurrence of godovikovite, millosevichite, steklite and an unnamed MgSO4, sometimes accompanied by subordinate admixtures of mikasaite, sabieite, efremovite, langbeinite and aphthitalite has been recorded from these locations. Occasionally they form monomineral aggregates, but usually occur as mixtures practically impossible to separate. The minerals form microcrystalline masses with a characteristic vesicular structure resembling a solidified foam or pumice. The sulfates crystallize from hot fire gases, similar to high temperature volcanic exhalations. The gases transport volatile components from the center of the fire but their chemical compositions are not yet known. Their cooling in the near-surface part of the heap results ...
Parafiniuk J. and Kruszewski Ł. (2009) — Am mo nium min er als from burn ing coal-dumps of the Up... more Parafiniuk J. and Kruszewski Ł. (2009) — Am mo nium min er als from burn ing coal-dumps of the Up per Silesian Coal Ba sin (Po land).
As sem blages com posed of 11 am mo nium min er als, mainly sulphates and chlo rides, were re cor... more As sem blages com posed of 11 am mo nium min er als, mainly sulphates and chlo rides, were re corded from four burn ing coal-dumps (BCD) in the Up per Silesian Coal Ba sin. Most of them are newly re corded from Po land. Min er als were iden ti fied us ing PXRD and SEM with EDS anal y ses. Salammoniac, NH4Cl, and tschermigite, (NH4)Al(SO4)2·12H2O are the most com mon spe cies on the BCD stud ied. Kremersite, (NH4,K)2[FeCl5(H2O)], is rare and co ex ists with mem bers of the ammonioalunite–ammoniojarosite se ries. Boussingaultite, (NH4)2Mg(SO4)2·6H2O, and more rarely clairite, (NH4)2Fe3(SO4)4(OH)3·3H2O, and mascagnite, (NH4)2SO4, ac com pany nu mer ous Mg, Al, Fe and Ca sul phate min er als. These usu ally oc cur as very fine ad mix tures form ing coat ings, small nod ules or po rous masses and were found on the BCD sur face close to gas vents. Also a mas sive sul phate crust was found in the deeper part of the BCD nearby the fire zone. This crust is com posed mainly of an hy drous sul...
X-ray diffraction studies of crystals under pressure and quantitative experimental charge density... more X-ray diffraction studies of crystals under pressure and quantitative experimental charge density analysis are among the most demanding types of crystallographic research. A successful feasibility study of the electron density in the mineral grossular under 1 GPa pressure conducted at the CRISTAL beamline at the SOLEIL synchrotron is presented in this work. A single crystal was placed in a diamond anvil cell, but owing to its special design (wide opening angle), short synchrotron wavelength and the high symmetry of the crystal, data with high completeness and high resolution were collected. This allowed refinement of a full multipole model of experimental electron distribution. Results are consistent with the benchmark measurement conducted without a diamond-anvil cell and also with the literature describing investigations of similar structures. Results of theoretical calculations of electron density distribution on the basis of dynamic structure factors mimic experimental findings ...
Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials
On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using a... more On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using an Ag source at 90 K to a resolution of 1.63 Å−1, a quantitative experimental charge density distribution has been obtained for fluorite (CaF2). The atoms-in-molecules integrated experimental charges for Ca2+ and F− ions are +1.40 e and −0.70 e, respectively. The derived electron-density distribution, maximum electron-density paths, interaction lines and bond critical points along Ca2+...F− and F−...F− contacts revealed the character of these interactions. The Ca2+...F− interaction is clearly a closed shell and ionic in character. However, the F−...F− interaction has properties associated with the recently recognized type of interaction referred to as `charge-shift' bonding. This conclusion is supported by the topology of the electron localization function and analysis of the quantum theory of atoms in molecules and crystals topological parameters. The Ca2+...F− bonded radii – measure...
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