Journal of Volcanology and Seismology

, Volume 7, Issue 6, pp 362–370 | Cite as

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

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

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 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) Å3. 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.

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Copyright information

© Pleiades Publishing, Ltd. 2013

Authors and Affiliations

  • G. A. Karpov
    • 1
  • S. V. Krivovichev
    • 2
  • L. P. Vergasova
    • 1
  • A. P. Chernyat’eva
    • 2
  • L. P. Anikin
    • 1
  • S. V. Moskaleva
    • 1
  • S. K. Filatov
    • 2
  1. 1.Institute of Volcanology and Seismology, Far East BranchRussian Academy of SciencesPetropavlovsk-KamchatskiiRussia
  2. 2.St. Petersburg UniversitySt. PetersburgRussia

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