Selenium Minerals: Structural and Chemical Diversity and Complexity

Кривовичев, В. Г.; Krivovichev, Sergey V.; Charykova, M. V.

doi:10.3390/min9070455

Cited by 16 publications

(22 citation statements)

References 58 publications

(90 reference statements)

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“…To quantify the chemical, structural and crystallochemical complexities of Te minerals, a total of pieces of 176 chemical composition data, and 117 data sets on crystal structure were reviewed. The level of structural complexity per atom ( str I G ) and per unit cell ( str I G,total ) [21][22][23][24][25][26] were calculated using the following equations [36]:…”

Section: Chemical Structural and Crystallochemical Complexitiesmentioning

confidence: 99%

“…In addition, it was shown that using the concept of mineral systems, it is possible to compare different geological objects with each other in terms of their mineral diversity [29][30][31][32]. Shannon information entropy (chemical and structural complexities) and the concepts of mineral systems have also been applied to mineral evolution as a whole [33][34][35] and to the mineral ecology of selenium minerals, including their diversity and complexities [36][37][38].…”

Section: Introductionmentioning

confidence: 99%

“…Previously, we have characterized selenium minerals and described their chemical and structural complexities [36][37][38]. The aim of this paper was to characterize Te minerals and to determine relations between their chemical, structural, and crystallochemical complexities, as well as to apply the data obtained to the understanding of Te mineral complexity and diversity.…”

Section: Introductionmentioning

confidence: 99%

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Tellurium Minerals: Structural and Chemical Diversity and Complexity

2020

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The chemical diversity and complexity of tellurium minerals were analyzed using the concept of mineral systems and Shannon informational entropy. The study employed data for 176 Te mineral species known today. Tellurium minerals belong to six mineral systems in the range of one-to-six species-defining elements. For 176 tellurium minerals, only 36 chemical elements act as essential species-defining constituents. The numbers of minerals of main elements are calculated as follows (the number of mineral species is given in parentheses): O (89), H (48), Cu (48), Pb (43), Bi (31), S (29), Ag (20), Fe (20), Pd (16), Cl (13), and Zn (11). In accordance with their chemistry, all Te minerals are classified into five types of mineral systems: tellurium, oxides, tellurides and intermetalides, tellurites, and tellurates. A statistical analysis showed positive relationships between the chemical, structural, and crystallochemical complexities and the number of essential species-defining elements in a mineral. A positive statistically significant relationship between chemical and structural complexities was established. It is shown that oxygen-free and oxygen-bearing Te minerals differ sharply from each other in terms of chemical and structural complexity, with the first group of minerals being simpler than the second group. The oxygen-free Te minerals (tellurium, tellurides, and intermetallides) are formed under reducing conditions with the participation of hydrothermal solutions. The most structurally complex oxygen-bearing Te minerals originate either from chemical weathering and the oxidation of ore deposits or from volcanic exhalations (Nabokoite).

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Section: Chemical Structural and Crystallochemical Complexitiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Tellurium Minerals: Structural and Chemical Diversity and Complexity

2020

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“…This approach suggested by S.V. Krivovichev [24] and recently successfully implemented in [25,26] allows the factors that influence the symmetry preservation or reduction of uranyl selenite units to be revealed, and it shows which of the multiple blocks plays the most important role in a particular structure formation.…”

Section: Complexity Calculationsmentioning

confidence: 99%

Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites

et al. 2019

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Comparison of the natural and synthetic phases allows an overview to be made and even an understanding of the crystal growth processes and mechanisms of the particular crystal structure formation. Thus, in this work, we review the crystal chemistry of the family of uranyl selenite compounds, paying special attention to the pathways of synthesis and topological analysis of the known crystal structures. Comparison of the isotypic natural and synthetic uranyl-bearing compounds suggests that uranyl selenite mineral formation requires heating, which most likely can be attributed to the radioactive decay. Structural complexity studies revealed that the majority of synthetic compounds have the topological symmetry of uranyl selenite building blocks equal to the structural symmetry, which means that the highest symmetry of uranyl complexes is preserved regardless of the interstitial filling of the structures. Whereas the real symmetry of U-Se complexes in the structures of minerals is lower than their topological symmetry, which means that interstitial cations and H 2 O molecules significantly affect the structural architecture of natural compounds. At the same time, structural complexity parameters for the whole structure are usually higher for the minerals than those for the synthetic compounds of a similar or close organization, which probably indicates the preferred existence of such natural-born architectures. In addition, the reexamination of the crystal structures of two uranyl selenite minerals guilleminite and demesmaekerite is reported. As a result of the single crystal X-ray diffraction analysis of demesmaekerite, Pb 2 Cu 5 [(UO 2 ) 2 (SeO 3 ) 6 (OH) 6 ](H 2 O) 2 , the H atoms positions belonging to the interstitial H 2 O molecules were assigned. The refinement of the guilleminite crystal structure allowed the determination of an additional site arranged within the void of the interlayer space and occupied by an H 2 O molecule, which suggests the formula of guilleminite to be written as Ba 3 . occurrence is limited to just a few localities. First, these are Musonoi and Shinkolobwe mines in DR Congo [6], two of the minerals were only found in the Repete mine (San Juan County, Utah, USA) [5], and a few more occurrences in Europe could be mentioned (small uranium deposit Zálesí in the Czech Republic, Liauzun in France, and La Creusaz U prospect in Switzerland) [8]. Nevertheless, apart from mineralogy, uranyl selenites are of great interest from the geochemical and radiochemical points of view. It is known that fission products contain 53 g per ton [9] of long-lived 79 Se isotope with a half-life of 1.1 × 10 6 years [10] after three years of nuclear fuel irradiation in the reactor. Thus, an understanding of the processes of mineral formation in nature and their synthetic analogs in laboratories can help in the processing of nuclear wastes. Crystal chemical and structural investigations are key points in such a material's scientific studies due to the essential knowledge of how the variation in the chemical composi...

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“…This approach, recently developed by S.V. Krivovichev [28][29][30] and successfully implemented in [22,31,32], allowed to compare the structures in terms of their information content and to analyze contributions of various substructural building blocks into the complexity of the whole structure. Structural complexity is a negative contribution to the configurational entropy of a crystalline compound and thus could help to understand and describe the processes of various structures formation in the laboratory and, what is of special interest, in nature.…”

Section: Structural Complexitymentioning

confidence: 99%

Crystallographic Insights into Uranyl Sulfate Minerals Formation: Synthesis and Crystal Structures of Three Novel Cesium Uranyl Sulfates

et al. 2019

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An alteration of the uranyl oxide hydroxy-hydrate mineral schoepite [(UO2)8O2(OH)12](H2O)12 at mild hydrothermal conditions was studied. As the result, four different crystalline phases Cs[(UO2)(SO4)(OH)](H2O)0.25 (1), Cs3[(UO2)4(SO4)2O3(OH)](H2O)3 (2), Cs6[(UO2)2(SO4)5](H2O)3 (3), and Cs2[(UO2)(SO4)2] (4) were obtained, including three novel compounds. The obtained Cs uranyl sulfate compounds 1, 3, and 4 were analyzed using single-crystal XRD, EDX, as well as topological analysis and information-based structural complexity measures. The crystal structure of 3 was based on the 1D complex, the topology of which was unprecedented for the structural chemistry of inorganic oxysalts. Crystal chemical analysis performed herein suggested that the majority of the uranyl sulfates minerals were grown from heated solutions, and the temperature range could be assumed from the manner of interpolyhedral linkage. The presence of edge-sharing uranyl bipyramids most likely pointed to the temperatures of higher than 100 °C. The linkage of sulfate tetrahedra with uranyl polyhedra through the common edges involved elevated temperatures but of lower values (~70–100 °C). Complexity parameters of the synthetic compounds were generally lower than that of uranyl sulfate minerals, whose structures were based on the complexes with the same or genetically similar topologies. The topological complexity of the uranyl sulfate structural units contributed the major portion to the overall complexity of the synthesized compounds, while the complexity of the respective minerals was largely governed by the interstitial structure and H-bonding system.

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Selenium Minerals: Structural and Chemical Diversity and Complexity

Cited by 16 publications

References 58 publications

Tellurium Minerals: Structural and Chemical Diversity and Complexity

Tellurium Minerals: Structural and Chemical Diversity and Complexity

Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites

Crystallographic Insights into Uranyl Sulfate Minerals Formation: Synthesis and Crystal Structures of Three Novel Cesium Uranyl Sulfates

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