Polymorphism and Isomorphic Substitutions in the \({\text{Cu}}_{3}^{{2 + }}\)(T 5+O4)2 Natural System with T = As, V, or P

Abstract—In the \({\text{Cu}}_{3}^{{2 + }}\)(T5+O4)2 (T = As, V or P) natural system arsenates are trimorphous (lammerite, lammerite-β, and unnamed triclinic Cu3[(As,V)O4]2), as well as vanadates (mcbirneyite, pseudolyonsite, and borisenkoite), while phosphates are represented by a poorly studied lammerite-like Cu3[(P,As)O4]2 phase. In active oxidizing-type fumaroles related to the Tolbachik volcano in Kamchatka, Russia, all these minerals crystallized at temperature no lower than 250°C. The crystal structure of natural triclinic Cu3[(As,V)O4]2 was first studied on a single crystal from the Yadovitaya fumarole at Tolbachik; R = 4.89%. It is isostructural to stranskiite and mcbirneyite and crystallizes in the P-1 space group; the unit-cell parameters are: a = 5.0701(8), b = 5.4047(8), c = 6.3910(8) Å, α = 70.091(13), β = 86.828(12), γ = 68.399(15)°, V = 152.61(4) Å3, and Z = 1. This paper also contains new data on mcbirneyite (its novel As-enriched variety is characterized), lammerite, and lammerite-β. Original and previously published materials on natural members of the Cu3(T5+O4)2 system are summarized and isomorphism and other crystal chemical features of minerals belonging to this system are discussed in comparison with the data on related synthetic compounds.

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Notes

  1. 1.

    The term “hydrogen-free,” which is not often used in the Russian literature, should be taken literally: a mineral does not contain any hydrogen species (OH, H2O0, cations H+ and H3O+ and others).

  2. 2.

    Crystal structures of oxysalts of this system including their comparison are discussed below.

  3. 3.

    More electron microprobe data for lammerite, lammerite-β, and borisenkoite are given in (Pekov et al., 2018а; Pekov et al., 2020).

  4. 4.

    In the original description of lammerite-β (Starova et al., 2012), only the Second cone of GFTE is given, while the name of the fumarole is not mentioned. According to Vergasova (pers. comm.), the holotype of this minerals comes from the Yadovitaya fumarole.

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Funding

This study was supported by the Russian Foundation for Basic Research (project no. 17-05-00179) [determination of the crystal structure of triclinic copper arsenate and study of isomorphic substitutions and solid solutions series in the Cu3(T5+O4)2] natural system and Russian Science Foundation (project no. 19-17-00050) [study of mcbirneyite mineralogy and crystal chemistry].

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Correspondence to I. V. Pekov.

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Translated by I. Baksheev

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Pekov, I.V., Zubkova, N.V., Yapaskurt, V.O. et al. Polymorphism and Isomorphic Substitutions in the \({\text{Cu}}_{3}^{{2 + }}\)(T 5+O4)2 Natural System with T = As, V, or P. Geol. Ore Deposits 62, 803–818 (2020). https://doi.org/10.1134/S1075701520080115

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Keywords:

  • copper arsenate
  • copper vanadate
  • polymorphism
  • lammerite
  • mcbirneyite
  • fumarole
  • Tolbachik volcano
  • Kamchatka