Mineral Systems,Their Types,and Distribution in Nature: 2. Products of Contemporary Fumarole Activity at Tolbachik Volcano (Russia) and Vulcano (Italy)

The number of mineral species in which a certain chemical element is species-defining (according to statistical data up to 2015) has been specified. Seventy chemical elements are species-defining for 5044 minerals. The following chemical elements lead in the composition of minerals (number of mineral species in parentheses): oxygen (4115), hydrogen (2800), silicon (1471), calcium (1167), sulfur (1056), aluminium (985), sodium (949), iron (945), copper (636), phosphorus (597), arsenic (594), and magnesium (571). The distribution of mineral species by various systems in the products of contemporary fumarole activity at two volcanoes, Tolbachik in Kamchatka, Russia, and Vulcano in Sicily, Italy, has been compared. These locations were also compared for the distribution of species-defining elements. Thus, it has been determined that in fumaroles of both volcanoes, Tl, S, Cl, F and Na are “excessive,” present in minerals in elevated amounts, whereas H, Ca, Fe, and Mn are “deficient.” The abundance of Cu, Se, V, Mg, Zn, As, and F in minerals at Tolbachik is higher than the global mean values of these elements in the Earth’s crust, whereas the abundance is significantly lower at Vulcano. Sn, I, Br, K, Pb, Al, Fe, and Bi demonstrate the opposite behavior. Comparison of the Yadovitaya and Arsenatnaya fumaroles at the Tolbachik volcano showed that the products of the former are richer in H, Cl, Cu, S, K, O, Al, Fe, and Pb, and poorer in As, Ca, Mg, and Na as species-defining elements. In addition, V-and Mo-bearing minerals are found only at Yadovitaya, whereas minerals containing F, Ti, В, Те, and Zn are known only at Arsenatnaya.     

Crystal chemistry of natural and synthetic lead oxyhalides. Part I. Crystal structure of Pb<Subscript>13</Subscript>O<Subscript>10</Subscript>Cl<Subscript>6</Subscript>

Crystals of lead oxychloride Pb₁₃O₁₀Cl₆ have been synthesized on the basis of high-temperature solid-state reactions. The Pb₁₃O₁₀Cl₆ structure was studied using X-ray single-crystal diffraction analysis. The compound is monoclinic, and the space group is C2/c; the unit-cell dimensions are a = 16.1699(14), b = 7.0086(6), c = 23.578(2) Å, β = 97.75°, and V = 2647.6(4) ų. The structure has been solved by direct methods and refined to R ₁ = 0.0505 for 2671 observed unique reflections. The structure is a 3D framework consisting of OPb₄ tetrahedrons. Chlorine atoms are located in the framework channels. The structure contains seven symmetrically independent Pb atoms, which are coordinated by 2 to 4 O^2? and 2 to 4 Cl^? anions. The synthesized compound is compared with other natural and synthetic lead oxyhalides.     

Refinement of the crystal structure of bonshtedtite, Na3Fe(PO4)(CO3)

The crystal structure of bonshtedtite, Na₃Fe(PO₄)(CO₃) (monoclinic, P2₁/m, a = 5.137(4), b = 6.644(4), c = 8.908(6) Å, β = 90.554(14)°, V = 304.0(4) ų, Z = 2) has been refined to R ₁ = 0.041 on the basis of 1314 unique reflections. The structure is similar to that of other minerals of the bradleyite group. It is based on the [Fe(PO₄)(CO₃)]^3? layers oriented parallel to (001). The layers are formed by corner-sharing PO₄ tetrahedra and FeO₄(CO₃) complexes, where FeO₆ tetrahedra and CO₃ triangles are edge-shared. The topology of the octa-tetrahedral layer in bonshtedtite is similar to that of the autunite-group minerals, but it differs from the latter in terms of local topological properties.     

Romanorlovite,a New Copper and Potassium Hydroxychloride from the Tolbachik Volcano,Kamchatka, Russia

A new mineral romanorlovite has been found in the upper, moderately hot zones of two fumaroles, Glavnaya Tenoritovaya (Major Tenorite) and Arsenatnaya (Arsenate), located at the second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with avdoninite in both fumaroles, and in Glavnaya Tenoritovaya, it is also associated with belloite, sylvite, carnallite, mitscherlichite, sanguite, chlorothionite, eriochalcite, chrysothallite, and mellizinkalite. Romanorlovite occurs as prismatic, equant, or tabular tetragonal crystals up to 0.1 mm in size, crystal clusters up to 0.5 mm, and crusts up to 2 × 2 mm in area. The mineral is transparent with vitreous luster. Its color varies from yellow-brown to dark brown, and tiny crystals are honey- or golden-yellow. Cleavage is not observed. Romanorlovite is brittle. The Mohs hardness is ca ~3. The calculated density varies from 2.72 to 2.79 g/cm³ depending on the content of admixed Pb. The mineral is optically uniaxial (–), ω = 1.727(3), ε = 1.694(2). The Raman spectrum has been reported. The chemical composition of the holotype sample (wt %; electron microprobe data, contents of О and H calculated by stoichiometry) is as follows: 21.52 K, 0.89 Pb, 28.79 Cu, 0.02 Zn, 44.74 Cl, 4.85 O_calc, 0.41 H_calc, total 101.22. Its empirical formula calculated based on Cl₂₅ with (ОН)₄(Н2О)₂ is K_10.90Pb_0.09Cu_8.97Zn_0.01Cl₂₅(OH)₄ · 2H₂O. The simplified formula is K₁₁Cu₉Cl₂₅(OH)₄ · 2H₂O (Z = 4). Romanorlovite is tetragonal, space group[ I4/mmm. The unit cell parameters are (1) holotype: a = 17.5804(7), c = 15.9075(6) Å, V = 4916.5(3) ų; (2) the sample enriched in Pb on which the crystal structure was refined: a = 17.5538(19), c = 15.8620(17) Å, V= 4887.7(9) ų. The strongest reflections of the powder XRD pattern (d, Å–I[hkl]) are 12.48–56[110], 11.74–36[101], 8.80–100[200], 7.97–34[002], 6.71–40[112], 3.165–32[512], 2.933–80[215, 433], 2.607–38[514]. The mineral is named in honor of Roman Yu. Orlov (1929-2005), Russian mineralogist and physicist, who worked in the Department of Mineralogy, Moscow State University.     

The crystal structure of loparite: a new acentric variety

Mineralogy and Petrology - The crystal structure of a new structural variety of loparite (Na0.56Ce0.21La0.14Ca0.06Sr0.03Nd0.02Pr0.01)Σ=1.03(Ti0.83Nb0.15)Σ=0.98O3 from the Khibiny alkaline...     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: I. Thermodynamic constants at ambient conditions

Understanding and deciphering processes proceeding near the surface are among the urgent tasks of contemporary mineralogy and geochemistry, which are especially important for resolving ecological challenges and developing principles of rational environmental management. The paper presents systematized data published on thermodynamics of minerals (arsenates, sulfates, selenites, and selenates), which are formed in the weathering zone of sulfide ores, and determines approaches to quantitative physicochemical modeling of their formation conditions. Diagrams of phase and chemical equilibria (Eh-pH, diagrams of solubility) of the subsystems of the model system Fe-Cu-Zn-Pb-Co-Ni-As-Se-S-H₂O (Fe²⁺, Fe³⁺, Cu²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, H⁺//SeO₃²⁻, SeO₄²⁻, AsO₄³⁻, SO₄²⁻, OH⁻-H₂O) are used as a thermodynamic basis for modeling mineral-forming processes in the weathering zone of ore deposits. Seventy-two arsenates, about 70 sulfates, and 7 selenites and selenates have been identified in the framework of this system. The available published values of standard thermodynamic functions of the formation of minerals and chemical compounds are given, as well as the Pitzer equation parameters to describe the sulfate systems, which are substantially specific due to the high solubility of their components.