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Dobrovolskyite, Na4Ca(SO4)3, is a new sulfate mineral from the Great Tolbachik fissure eruption, Kamchatka peninsula, Russia. It occurs as aggregates of tabular crystals up to 1–2 mm in maximum dimension, with abundant gas inclusions. The empirical formula calculated on the basis of O = 12 is (Na3.90K0.10)Σ4(Ca0.45Mg0.16Cu0.12Na0.10)Σ0.83S3.08O12. The crystal structure of dobrovolskyite was determined using single-crystal X-ray diffraction data as: trigonal, R3, a = 15.7223(2), c = 22.0160(5) Å, V = 4713.1(2) Å3, Z = 18 and R1 = 0.072. The Mohs’ hardness is 3.5. The mineral is uniaxial (+), with ω = 1.489(2) and ɛ = 1.491(2) (λ = 589 nm). The seven strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 11.58(40)(101); 5.79(22)(202); 4.54(18)(030); 3.86(88)(033); 3.67(32)(006); 2.855(50)(306); and 2.682(100)(330). The mineral is named in honour of Prof. Dr. Vladimir Vitalievich Dolivo-Dobrovolsky (1927–2009), one of the leading Russian scientists in the field of petrology, crystal optics and crystal chemistry. The crystal structure of dobrovolskyite can be described as composed of three symmetrically independent rods running parallel to the c axis. The rods consist of six octahedral–tetrahedral [Na(SO4)6]11– or [Ca(SO4)6]10– clusters of central octahedra sharing common corners with six adjacent SO4 tetrahedra. Alternatively, the crystal structure of the mineral can be described as a 12-layer ABACABACABAC eutactic array of Na+ and Ca2+ cations, and vacancies with disordered (SO4) tetrahedra in interstices. Dobrovolskyite and similar minerals probably formed upon cooling of a high-temperature phase with disordered cation and anion arrangements.
Belomarinaite, ideally KNaSO4, is a new sulfate mineral discovered in the Toludskoe lava field, formed during the 2012–2013 Tolbachik Fissure eruption. The mineral occurs as arborescent aggregates of tabular crystals (1 mm × 0.3 mm × 0.1 mm) comprising hematite impurities. The average size of the aggregates is 0.5–0.7 mm. The empirical formula is (K0.95Na0.92Cu0.04)Σ1.91S1.01O4. The crystal structure of belomarinaite was determined using single-crystal X-ray diffraction data; the space group is P3m1, a = 5.6072(3), c = 7.1781(4) Å, V = 195.45(2) Å3, Z = 2 and R1 = 2.6%. In the crystal structure of belomarinaite, there are six cation sites: the S1 and S2 sites are occupied by S, the Na and K sites are occupied by Na and K, respectively, giving Na0.5K0.5 apfu and the M1 and M2 sites are occupied by Na0.78K0.22 and K0.78Na0.22 apfu, respectively. The crystal structure is a framework of SO4 tetrahedra, Na octahedra and K, M1 and M2 polyhedra. Belomarinaite is isostructural with the synthetic compound KNaSO4. In belomarinaite, Na and K are disordered over M1 and M2 sites; in its synthetic analogue, Na and K are ordered over M1 and M2 sites, respectively. The Mohs’ hardness is 2–3. The mineral is uniaxial (+), with ω = 1.485(3) and ε = 1.488(3) (λ = 589 nm). The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 4.022(31)(101); 3.591(26)(002); 2.884(74)(102); 2.800(100)(110); 2.391(16)(003); 2.296(8)201; 2.008(38)(022); and 1.634(10)(212). The mineral was named in honour of Russian volcanologist Marina Gennadievna Belousova (b. 1960) for her significant contributions to the monitoring of the Tolbachik Fissure eruption.
The new mineral saranchinaite, ideally Na2Cu(SO4)2, was found in sublimates of the Saranchinaitovaya fumarole, Naboko Scoria Cone, Tolbachik volcano, Kamchatka, Russia. Its discovery and study has enabled the characterization of the thermal decomposition of kröhnkite and provided an insight into the high-temperature behaviour of other kröhnkite-type materials. Saranchinaite is monoclinic, P21, a = 9.0109(5), b = 15.6355(8), c = 10.1507(5) Å, β = 107.079(2)°, V = 1367.06(12) Å3, Z = 8 and R1 = 0.03. Saranchinaite is a unique mineral in that two of its four independent Cu sites display a very unusual Cu2+ coordination environment with two weak Cu–O bonds of ~2.9–3.0 Å, resulting in [4+1+2] CuO7 polyhedra. Each of the Cu-centred polyhedra shares common corners with SO4 tetrahedra resulting in a [Cu4(SO4)8]8– framework with a complex channel system occupied by Na atoms. Saranchinaite is sensitive to moisture and transforms into kröhnkite within one week when exposed to open air at 87% relative humidity and 25°C. High-temperature X-ray diffraction studies were performed for both kröhnkite (from La Vendida mine, Antofagasta Region, Chile) and saranchinaite. During thermal expansion kröhnkite retains its strongly anisotropic character up to its full dehydration and the formation of saranchinaite at ~200°C, which then transforms back into kröhnkite after exposure to open air. The thermal expansion of saranchinaite is more complex than that of kröhnkite. Saranchinaite is stable up to 475°C with subsequent decomposition into tenorite CuO, thénardite Na2SO4 and unidentified phases.
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