Copper in Natural Oxide Spinels: The New Mineral Thermaerogenite CuAl2O4, Cuprospinel and Cu-Enriched Varieties of Other Spinel-Group Members from Fumaroles of the Tolbachik Volcano, Kamchatka, Russia

Abstract

This paper is the first description of natural copper-rich oxide spinels. They were found in deposits of oxidizing-type fumaroles related to the Tolbachik volcano, Kamchatka, Russia. This mineralization is represented by nine species with the following maximum contents of CuO (wt.%, given in parentheses): a new mineral thermaerogenite, ideally CuAl2O4 (26.9), cuprospinel, ideally CuFe3+2O4 (28.6), gahnite (21.4), magnesioferrite (14.7), spinel (10.9), magnesiochromite (9.0), franklinite (7.9), chromite (5.9), and zincochromite (4.8). Cuprospinel, formerly known only as a phase of anthropogenic origin, turned out to be the Cu-richest natural spinel-type oxide [sample with the composition (Cu0.831Zn0.100Mg0.043Ni0.022)Σ0.996(Fe3+1.725Al0.219Mn3+0.048Ti0.008)Σ2.000O4 from Tolbachik]. Aluminum and Fe3+-dominant spinels (thermaerogenite, gahnite, spinel, cuprospinel, franklinite, and magnesioferrite) were deposited directly from hot gas as volcanic sublimates. The most probable temperature interval of their crystallization is 600–800 °C. They are associated with each other and with tenorite, hematite, orthoclase, fluorophlogopite, langbeinite, calciolangbeinite, aphthitalite, anhydrite, fluoborite, sylvite, halite, pseudobrookite, urusovite, johillerite, ericlaxmanite, tilasite, etc. Cu-bearing spinels are among the latest minerals of this assemblage: they occur in cavities and overgrow even alkaline sulfates. Cu-enriched varieties of chrome-spinels (magnesiochromite, chromite, and zincochromite) were likely formed in the course of the metasomatic replacement of a magmatic chrome-spinel in micro-xenoliths of ultrabasic rock under the influence of volcanic gases. The new mineral thermaerogenite, ideally CuAl2O4, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption. It forms octahedral crystals up to 0.02 mm typically combined in open-work clusters up to 1 mm across. Thermaerogenite is semitransparent to transparent, with a strong vitreous lustre. Its colour is brown, yellow-brown, red-brown, brown-yellow or brown-red. The mineral is brittle, with the conchoidal fracture, cleavage is none observed. D(calc.) is 4.87 g/cm3. The chemical composition of the holotype (wt.%, electron microprobe) is: CuO 25.01, ZnO 17.45, Al2O3 39.43, Cr2O3 0.27, Fe2O3 17.96, total 100.12 wt.%. The empirical formula calculated on the basis of 4 O apfu is: (Cu0.619Zn0.422)Σ1.041(Al1.523Fe3+0.443Cr0.007)Σ1.973O4. The mineral is cubic, Fd-3m, a = 8.093(9) Å, V = 530.1(10) Å3. Thermaerogenite forms a continuous isomorphous series with gahnite. The strongest lines of the powder X-ray diffraction pattern of thermaerogenite [d, Å (I, %) (hkl)] are: 2.873 (65) (220), 2.451 (100) (311), 2.033 (10) (400), 1.660 (16) (422), 1.565 (28) (511) and 1.438 (30) (440).

High‐temperature gold‐copper extraction with chloride flux in lava tubes of Tolbachik volcano (Kamchatka)

“…The recorded Cu‐bearing magnesioferrite in a close association with tenorite and hematite (Figure f; Figure S6, S7; also see Pekov et al, for details of Cu‐enriched spinel assemblage in fumaroles of the Tolbachik volcano) has analogues in operating base metal smelters worldwide (e.g. Schlesinger, King, Sole, & Davenport, ).…”

Deltalumite, a new natural modification of alumina with spinel-type structure

“…Именно последний представляется наиболее вероятным источником алюминия, имеющего низкую летучесть в вулканическом газе даже при температурах выше 500 ºC (Symonds, Reed, 1993). Отметим, что находки корунда и высокоглиноземистых оксидов группы шпинели не являются редкостью для высокотемпературных (600-800 ºC) фумарол Толбачика (Pekov et al, 2014(Pekov et al, , 2018. Возможно, дельталюмит самостоятельно кристаллизовался при этих температурах или же явился продуктом преобразования ранее возникших глиноземистых минералов (бёмита?…”

Editorial for Special Issue “New Mineral Species and Their Crystal Structures”

“…Recently an increasing number of new mineral species discovered in volcanic fumaroles has been observed [1]. In the present issue, there are two articles devoted to the two new volcanic minerals: Verneite, Na 2 Ca 3 Al 2 F 14 , described simultaneously from Eldfell and Hekla volcanoes in Iceland and Vesuvius in Italy [2], and thermaerogenite, CuAl 2 O 4 , from the Tolbachik volcano at Kamchatka, Russia [3]. In these articles, readers could not only find the high level of the analytical investigation, but also the authors' imagination with regards to the choice of names for the new minerals:…”

“…Their definition indicates that, they are: (1) naturally occurring; (2) belonging to the distinct structural type; (3) stable, varying merely in the relatively small limits of chemical composition. If a given mineral differs from other known species in its structure (2) and/or composition (3) then it can be considered as a new mineral species.…”

“…Greek words , hot, , gas, and that means "born by". Thus, in whole it means born by hot gas, that reflects the fumarolic origin of the mineral" [3].…”