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


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2013-11

AUTHORS

G. A. Karpov, S. V. Krivovichev, L. P. Vergasova, A. P. Chernyat’eva, L. P. Anikin, S. V. Moskaleva, S. K. Filatov

ABSTRACT

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 Na2.22K5.47Cu8.02S8.05O36. 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) Å3. The crystal structure was determined by direct techniques and refined to yield R1 for 3955 reflexes//web// with F2 > 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) Å3. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R1 = 0.135 for 4088 reflexes with F2 > 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. More... »

PAGES

362-370

Identifiers

URI

http://scigraph.springernature.com/pub.10.1134/s0742046313060031

DOI

http://dx.doi.org/10.1134/s0742046313060031

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1041151325


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