New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. I. Yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6

Abstract

AbstractA new mineral, yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6, occurs in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with hatertite, bradaczekite, johillerite, hematite, tenorite, tilasite and aphthitalite. Yurmarinite occurs as well-shaped, equant crystals up to 0.3 mm in size, their clusters up to 0.5 mm and thin, interrupted crystal crusts up to 3 mm × 3 mm on volcanic scoria. Crystal forms are {101}, {011}, {100}, {110} and {001}. Yurmarinite is transparent, pale green or pale yellowish green to colourless. The lustre is vitreous and the mineral is brittle. The Mohs hardness is ∼4½. One direction of imperfect cleavage was observed, the fracture is uneven. D(calc.) is 4.00 g cm−3. Yurmarinite is optically uniaxial (−), ω = 1.748(5), ε = 1.720(3). The Raman spectrum is given. The chemical composition (wt.%, electron microprobe data) is Na2O 16.85, K2O 0.97, CaO 1.28, MgO 2.33, MnO 0.05, CuO 3.17, ZnO 0.97, Al2O3 0.99, Fe2O3 16.44, TiO2 0.06, P2O5 0.12, V2O5 0.08, As2O5 56.68, total 99.89. The empirical formula, calculated on the basis of 24 O atoms per formula unit, is (Na6.55Ca0.28K0.22)S7.05(Fe2.483+Mg0.70Cu0.48Al0.23Zn0.14Ti0.01Mn0.01)S4.05(As5.94P0.02V0.01)S5.97O24. Yurmarinite is rhombohedral, Rc, a = 13.7444(2), c = 18.3077(3) Å, V = 2995.13(8) Å3, Z = 6. The strongest reflections in the X-ray powder pattern [d, Å (I)(hkl)] are: 7.28(45)(012); 4.375(33)(211); 3.440(35)(220); 3.217(36)(131,214); 2.999(30)(223); 2.841(100)(125); 2.598(43)(410). The crystal structure was solved from single-crystal X-ray diffraction data to R = 0.0230. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters (M = Fe3+ > Mg,Cu) linked with AsO4 tetrahedra. Sodium atoms occupy two octahedrally coordinated sites in the voids of the framework. In terms of structure, yurmarinite is unique among minerals but isotypic with several synthetic compounds with the general formula (Na7–x☐x)(M3+x3+M1–x2+)(T5+O4)2 in which T = As or P, M3+ = Fe or Al, M2+ = Fe and 0 ≤ x ≤ 1. The mineral is named in honour of the Russian mineralogist, petrologist and specialist in studies of ore deposits, Professor Yuriy B. Marin (b. 1939). The paper also contains a description of the Arsenathaya fumarole and an overview of arsenate minerals formed in volcanic exhalations.