Thermodynamics of arsenates,selenites and sulfates in the oxidation zone of sulfide ores: XII. Mineral equilibria in the Cd–Se–H<Subscript>2</Subscript>O system at 25°C

Understanding the mechanisms of cadmium and selenium behavior under near-surface conditions is very important for solving certain environmental problems. The principal aim of this study is physicochemical analysis of the formation conditions of synthetic cadmium selenite CdSeO₃ · H₂O and experimental investigation of its thermal stability and dehydration and dissociation mechanisms. The synthesis was performed by boiling-dry aqueous solutions of cadmium nitrate and sodium selenite. The obtained samples were identified with electron microprobe and powder X-ray diffraction. Complex thermal analysis (thermogravimetry and differential scanning calorimetry) have shown that CdSeO₃ · H₂O is dehydrated at 177–241°C in two stages, apparently corresponding to the formation of CdSeO₃ · 2/3H₂O. The Eh–pH diagrams were calculated using the Geochemist’s Workbench (GWB 9.0) software package. The Eh–pH diagrams have been calculated for the Cd–Se–Н₂О and Cd–Se–CO₂–H₂O systems for the average content of these elements in underground waters. The formation of cadmium selenite, CdSeO₃ · H₂O in the oxidation medium is quite possible. The existence of CdSeO₃ is possible at high temperature.     

Diamonds in lavas of the Tolbachik fissure eruption in Kamchatka

Diamond crystals 0.05–0.2 mm (rarely up to 0.7 mm) in size were found in lavas of the Tolbachik fissure eruption (TFE, Kamchatka, 2012–2013). The TFE basaltic lavas with diamonds in the pores are similar in chemical composition to the lavas of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka, 1975–1976); however, the basalts of the new eruption contain slightly more SiO₂ and higher Fe relative to those of GTFE. Basalts of both eruptions are close in trace element composition. The diamonds were identified using electron microscopy and X-ray diffraction. The crystals, as a rule, represent a combination of cubes and octahedrons, with rare rhombododecahedrons. The TFE diamond has a typical cubic cell with a cube edge a = 3.574 Å and belongs to the spatial group of Fd-3m. The X-ray diffraction pattern of some grains contain reflexes with fractional indices, which indicate the twinning of the diamond along the plane {111}, which is confirmed by crystal morphological analysis. The TFE diamond was formed at the early stage of eruption with typical intense gaseous-pyroclastic jets to a height of 250 m and more. The finding of diamonds in fresh products of basaltic eruption of an active volcano may be considered as evidence of its magmatic source. Such numerous (hundreds) diamond grains in lavas of the active volcano were found for the first time in the world.     

Modular nature of the polysomatic pyrochlore-murataite series

Synthetic analogues of murataite, a very rare mineral—a complex oxide of REE, actinide, Ti, Fe, and other elements,—are of great interest as confinement matrices of radioactive wastes. They are produced by sintering (1200–1300°C) and melting (1500–1600°C) with subsequent crystallization of the melt. Four structural varieties of murataite distinguished by unit-cell parameters have been established by TEM study. All these varieties are derivatives of the fluorite structure designated as murataite 3C, 5C, 7C, and 8C depending on repetition factor of a parameter of the fluorite subcell. The structural features of the synthetic murataite varieties are analyzed in this paper based on data obtained from high-resolution electron microscopy, microdiffraction, and X-ray refinement. The hypothesis of a modular structure of the members of polysomatic pyrochlore-murataite series has been confirmed. At the same time, the structural modules are zero-dimensional rather than two-dimensional as had previously been suggested. The combinations of zero-dimensional modules in 3D space create the entire structural diversity of the polysomatic series.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: IV. Eh-pH diagrams of the Me-Se-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of selenium at the Earth’s surface and nearby at low temperatures and pressures is controlled by variations of the redox potential and the acidity of solutions. These parameters determine the migration of selenium and its precipitation as various solid phases. Understanding the mechanism of selenium’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with selenium (a _ΣSe = 10⁻⁹, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻⁵–10⁻⁴, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-Se-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in underground water and for their contents in oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb selenites and selenates at the surface is discussed.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: Part III: Eh-pH diagrams of the Me-As-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a _ΣAs = 3 × 10⁻⁸, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻³, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.     

Oxysulfates of copper, sodium, and potassium in the lava flows of the 2012–2013 Tolbachik Fissure Eruption

Samples from the surface of lava flows discharged by the 2012–2013 Tolbachik Fissure Eruption were found to contain oxysulfates of copper, sodium, and potassium: K₂Cu₃O(SO₄)₂ (fedotovite), NaKCu₂O(SO₄)₂, and Na₃K₅Cu₈O₄(SO₄)₈. The last two phases have no naturally occurring or synthetic analogues that we are aware of. They form flattened crystals of prismatic to long-prismatic habits. The crystals of Na₃K₅Cu₈O₄(SO₄)₈ have a chemical composition corresponding to the empirical formula Na_2.22K_5.47Cu_8.02S_8.05O₃₆. An X-ray analysis of this compound showed that it has a monoclinic symmetry, P2/c, a = 13.909(4), b = 4.977(1), c = 23.525(6) Å, β = 90.021(5)°, V = 1628.3(7) ų. The crystal structure was determined by direct techniques and refined to yield R ₁ for 3955 reflexes//web// with F ² > 4σF. The compound NaKCu₂O(SO₄)₂ also belongs to the monoclinic system, P2/c, a = 14.111(4), b = 4.946(1), c = 23.673(6) Å, β = 92.052(6)°, V = 1651.1(8) ų. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R ₁ = 0.135 for 4088 reflexes with F ² > 4σF. The crystal structure of Na₃K₅Cu₈O₄(SO₄)₈ is based on chains of [O₂Cu₄]⁴⁺ consisting of rib-coupled oxy-centered tetrahedrons of (OCu₄)⁶⁺. The chains are surrounded by sulfate radicals, resulting in columns of {[O₂Cu₄](SO₄)₄}^4? aligned along the b axis. The interchain space contains completely ordered positions of Na⁺ and K⁺ cations. The principle underlying the connection of NaKCu₂O(SO₄)₂ columns in the crystal structure of {[O₂Cu₄](SO₄)₄}^4? is different, in view of the relation Na:K = 1 as contrasted with 3:5 for the compound Na₃K₅Cu₈O₄(SO₄)₈. The presence of oxy-centered tetrahedrons in the structure of these new compounds furnishes an indirect hint at the importance of polynuclear copper-oxygen radicals with centering oxygen atoms as forms of transport of copper by volcanic gases.     

Alumovesuvianite,Ca19Al(Al,Mg)12Si18O69(OH)9, a new vesuvianite-group member from the Jeffrey mine,asbestos, Estrie region,Québec,Canada

Mineralogy and Petrology - Alumovesuvianite (IMA 2016–014), ideally Ca19Al(Al,Mg)12Si18O69(OH)9, is a new vesuvianite-group member found in the rodingite zone at the contact of a gabbroid...     

Crystal Chemistry of Pyroaurite from the Kovdor Pluton,Kola Peninsula,Russia, and the Långban Fe–Mn deposit,Värmland,Sweden

Pyroaurite [Mg₆Fe₂³⁺ (OH)₁₆][(CO₃)(H₂O)] from the Kovdor Pluton on the Kola Peninsula, Russia, and the Långban deposit in Filipstad, Värmland, Sweden were studied with single crystal and powder X-ray diffraction, an electron microprobe, and Raman spectroscopy. Both samples are rhombohedral, space group R3?m, a = 3.126(3), c = 23.52(2) Å (Kovdor), and a = 3.1007(9), c = 23.34(1) (Långban). The powder XRD revealed only the 3R polytype. The ratio of di- and trivalent cations M²⁺: M³⁺ was determined as ~3.1–3.2 (Kovdor) and ~3.0 (Långban). The Raman spectroscopy of the Kovdor sample verified hydroxyl groups and/or water molecules in the mineral (absorption bands in the region of 3600–3500 cm^–1) and carbonate groups (absorption bands in the region of 1346–1058 cm^–1). Based on the data obtained, the studied samples should be identified as pyroaurite-3R (hydrotalcite group).     

Mineral and Physicochemical Systems of Evaporites: Geochemical and Thermodynamic Aspects

The distribution of mineral species by various systems in evaporites from Inder Lake (Kazakhstan) and Searles Lake (United States) is compared, and these localities are compared in terms of the distribution of species-defining elements. Ca, K, Na, Cl, B, and S are excess elements whose contents are high in both localities, whereas Si and Al are deficient. It is shown that comprehensive analysis of the evaporite mineralogy with selection of species-defining elements (mineral systems) can be used as an objective base for constructing quantitative physicochemical models on the formation of various types of evaporites. In addition, this approach allows a better understanding of the formation conditions of certain solid phases (including crystalline hydrates), which have been synthesized in aqueous–salt systems but have not yet been found in nature.