Selenium Minerals: Structural and Chemical Diversity and Complexity

Chemical diversity of minerals containing selenium as an essential element has been analyzed in terms of the concept of mineral systems and the information-based structural and chemical complexity parameters. The study employs data for 123 Se mineral species approved by the International Mineralogical Association as of 25 May 2019. All known selenium minerals belong to seven mineral systems with the number of essential components ranging from one to seven. According to their chemical features, the minerals are subdivided into five groups: Native selenium, oxides, selenides, selenites, and selenates. Statistical analysis shows that there are strong and positive correlations between the chemical and structural complexities (measured as amounts of Shannon information per atom and per formula or unit cell) and the number of different chemical elements in a mineral. Analysis of relations between chemical and structural complexities provides strong evidence that there is an overall trend of increasing structural complexity with the increasing chemical complexity. The average structural complexity for Se minerals is equal to 2.4(1) bits per atom and 101(17) bits per unit cell. The chemical and structural complexities of O-free and O-bearing Se minerals are drastically different with the first group being simpler and the second group more complex. The O-free Se minerals (selenides and native Se) are primary minerals; their formation requires reducing conditions and is due to hydrothermal activity. The O-bearing Se minerals (oxides and oxysalts) form in near-surface environment, including oxidation zones of mineral deposits, evaporites and volcanic fumaroles. From the structural viewpoint, the five most complex Se minerals are marthozite, Cu(UO2)3(SeO3)2O2·8H2O (744.5 bits/cell); mandarinoite, Fe2(SeO3)3·6H2O (640.000 bits/cell); carlosruizite, K6Na4Na6Mg10(SeO4)12(IO3)12·12H2O (629.273 bits/cell); prewittite, KPb1.5ZnCu6O2(SeO3)2Cl10 (498.1 bits/cell); and nicksobolevite, Cu7(SeO3)2O2Cl6 (420.168 bits/cell). The mechanisms responsible for the high structural complexity of these minerals are high hydration states (marthozite and mandarinoite), high topological complexity (marthozite, mandarinoite, carlosruizite, nicksobolevite), high chemical complexity (prewittite and carlosruizite), and the presence of relatively large clusters of atoms (carlosruizite and nicksobolevite). In most cases, selenium itself does not play the crucial role in determining structural complexity (there are structural analogues or close species of marthozite, mandarinoite, and carlosruizite that do not contain Se), except for selenite chlorides, where stability of crystal structures is adjusted by the existence of attractive Se–Cl closed-shell interactions impossible for sulfates or phosphates. Most structurally complex Se minerals originate either from relatively low-temperature hydrothermal environments (as marthozite, mandarinoite, and carlosruizite) or from mild (500–700 °C) anhydrous gaseous environments of volcanic fumaroles (prewittite, nicksobolevite)

The Thermodynamics of Selenium Minerals in Near-Surface Environments

Selenium compounds are relatively rare as minerals; there are presently only 118 known mineral species. This work is intended to codify and systematize the data of mineral systems and the thermodynamics of selenium minerals, which are unstable (selenides) or formed in near-surface environments (selenites), where the behavior of selenium is controlled by variations of the redox potential and the acidity of solutions at low temperatures and pressures. These parameters determine the migration of selenium and its precipitation as various solid phases. All selenium minerals are divided into four groups—native selenium, oxide, selenides, and oxysalts—anhydrous selenites (I) and hydrous selenites and selenates (II). Within each of the groups, minerals are codified according to the minimum number of independent elements necessary to define the composition of the mineral system. Eh–pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 9.0) software package. The Eh–pH diagrams of the Me–Se–H2O systems (where Me = Co, Ni, Fe, Cu, Pb, Zn, Cd, Hg, Ag, Bi, As, Sb, Al and Ca) were plotted for the average contents of these elements in acidic waters in the oxidation zones of sulfide deposits. The possibility of the formation of Zn, Cd, Ag and Hg selenites under natural oxidation conditions in near surface environments is discussed

Raman spectroscopic characterization of the copper, cobalt, and nickel selenites: Synthetic analogs of chalcomenite, cobaltomenite, and ahlfeldite

<p>Raman spectroscopy has been used to study synthetic analogs of the minerals chalcomenite, cobaltomenite, and ahlfeldite occurring in nature. The results obtained are compared with the spectra of these minerals. In general, the majority of vibrational bands of synthetic species are in good agreement with natural chalcomenite, cobaltomenite, and ahlfeldite. The noticeable discrepancies are found for the bands assigned to the deformation mode of selenite groups. A better signal-to-noise ratio realized with synthetic species aids in comprehensive analysis of the spectra, especially in the region of water bands.</p

Mixed Uranyl Sulfate–Selenates: Evolution of Structural Topology and Complexity vs Chemical Composition

Phase formation in the aqueous system of uranyl nitrate, potassium hydroxide, and variable amounts of sulfuric and selenic acids has been investigated. Four different types of crystalline phases with variable S and Se contents were isolated and characterized using single-crystal X-ray diffraction (XRD) and IR spectroscopy. Topological analysis and information-based complexity calculations demonstrated the following: (a) the absence of a continuous solid solution in the system, (b) the absence of isotypic sulfate and selenate phases, and (c) the discovery of two layered topologies unprecedented among inorganic oxysalts

Xenophyllite, Na4Fe7(PO4)6, an Exotic Meteoritic Phosphate: New Mineral Description, Na-ions Mobility and Electrochemical Implications

Xenophyllite, ideally Na4Fe7(PO4)6, is a rare meteoritic phosphate found in phosphide-phosphate assemblages confined to troilite nodules of the Augustinovka iron meteorite (medium octahedrite, IIIAB). The mineral occurs as tiny lamella up to 0.15 mm long cross-cutting millimeter-sized grains of sarcopside, Fe3(PO4)2, associated with schreibersite, chromite and pentlandite. Xenophyllite is translucent, has a bluish-green to grey-green color and vitreous lustre. Moh’s hardness is 3.5–4. Cleavage is perfect on {001}. Measured density is 3.58(5) g/cm3. The mineral is biaxial (−), 2V 10–20°, with refractive indexes: α 1.675(2), β 1.681(2), γ 1.681 (2). Chemical composition of the holotype specimen (electron microprobe, wt.%) is: Na2O 10.9, K2O 0.4, MnO 5.8, FeO 42.1, Cr2O3 0.8, P2O5 40.7, total 100.7, corresponding to the empirical formula (Na3.67K0.09)Σ3.76(Fe2+6.12Mn2+0.85Cr0.11)Σ7.08P5.99O24.00. Xenophyllite is triclinic, P1 or P-1, a 9.643(6), b 9.633(5), c 17.645(11) Å; α 88.26(5), β 88.16(5), γ 64.83(5)°, V 1482(2) Å3, Z = 3. The toichiome C-centered subcell has the following dimensions: a 16.257(9), b 10.318(8), c 6.257(9) Å, β = 112.77(9)°, V 968(2) Å3, Z = 2. Xenophyllite is structurally related to synthetic phosphate Kna3Fe7(PO4)6 having a channel-type structure, and galileiite, NaFe4(PO4)3. The variations of chemical composition of xenophyllite ranging from Na4Fe7(PO4)6 to almost Na2Fe8(PO4)6 are accounted for by Na-ions mobility. The latter property makes xenophyllite a promising prototype for cathode materials used in sodium-ion batteries

Dmisteinbergite, CaAl2Si2O8, a Metastable Polymorph of Anorthite: Crystal-Structure and Raman Spectroscopic Study of the Holotype Specimen

The crystal structure of dmisteinbergite has been determined using crystals from the type locality in Kopeisk city, Chelyabinsk area, Southern Urals, Russia. The mineral is trigonal, with the following structure: P312, a = 5.1123(2), c = 14.7420(7) Å, V = 333.67(3) Å3, R1 = 0.045, for 762 unique observed reflections. The most intense bands of the Raman spectra at 327s, 439s, 892s, and 912s cm −1 correspond to different types of tetrahedral stretching vibrations: Si–O, Al–O, O–Si–O, and O–Al–O. The weak bands at 487w, 503w, and 801w cm−1 can be attributed to the valence and deformation modes of Si–O and Al–O bond vibrations in tetrahedra. The weak bands in the range of 70–200 cm−1 can be attributed to Ca–O bond vibrations or lattice modes. The crystal structure of dmisteinbergite is based upon double layers of six-membered rings of corner-sharing AlO4 and SiO4 tetrahedra. The obtained model shows an ordering of Al and Si over four distinct crystallographic sites with tetrahedral coordination, which is evident from the average &lt;T–O&gt; bond lengths (T = Al, Si), equal to 1.666, 1.713, 1.611, and 1.748 Å for T1, T2, T3, and T4, respectively. One of the oxygen sites (O4) is split, suggesting the existence of two possible conformations of the [Al2Si2O8]2− layers, with different systems of ditrigonal distortions in the adjacent single layers. The observed disorder has a direct influence upon the geometry of the interlayer space and the coordination of the Ca2 site. Whereas the coordination of the Ca1 site is not influenced by the disorder and is trigonal antiprismatic (distorted octahedral), the coordination environment of the Ca2 site includes disordered O atoms and is either trigonal prismatic or trigonal antiprismatic. The observed structural features suggest the possible existence of different varieties of dmisteinbergite that may differ in: (i) degree of disorder of the Al/Si tetrahedral sites, with completely disordered structure having the P63/mcm symmetry; (ii) degree of disorder of the O sites, which may have a direct influence on the coordination features of the Ca2+ cations; (iii) polytypic variations (different stacking sequences and layer shifts). The formation of dmisteinbergite is usually associated with metastable crystallization in both natural and synthetic systems, indicating the kinetic nature of this phase. Information-based complexity calculations indicate that the crystal structures of metastable CaAl2Si2O8 polymorphs dmisteinbergite and svyatoslavite are structurally and topologically simpler than that of their stable counterpart, anorthite, which is in good agreement with Goldsmith’s simplexity principle and similar previous observations