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Copper-Containing Magnesioferrite in Vesicular Trachyandesite in a Lava Tube from the 2012–2013 Eruption of the Tolbachik Volcano, Kamchatka, Russia

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Copper-Containing Magnesioferrite in Vesicular Trachyandesite in a Lava Tube from the 2012–2013 Eruption of the Tolbachik Volcano, Kamchatka, Russia minerals Article Copper-Containing Magnesioferrite in Vesicular Trachyandesite in a Lava Tube from the 2012–2013 Eruption of the Tolbachik Volcano, Kamchatka, Russia Victor V. Sharygin 1,2,3,* , Vadim S. Kamenetsky 4,5 , Liudmila M. Zhitova 1,2, Alexander B. Belousov 6 and Adam Abersteiner 5 1 V.S. Sobolev Institute of Geology and Mineralogy, Novosibirsk 630090, Russia; [email protected] 2 Department of Geology and Geophysics, Novosibirsk State University, Novosibirsk 630090, Russia 3 Institute of Physics and Technology, Ural Federal University, Ekaterinburg 620002, Russia 4 Institute of Experimental Mineralogy, Chernogolovka 142432, Russia; [email protected] 5 School of Natural Sciences, University of Tasmania, Hobart, TAS 7001, Australia; [email protected] 6 Institute of Volcanology and Seismology, Petropavlovsk-Kamchatsky 683006, Russia; [email protected] * Correspondence: [email protected]; Tel.: +7-383-330-80-84 Received: 13 October 2018; Accepted: 5 November 2018; Published: 8 November 2018 Abstract: Cu-rich magnesioferrite was found in vesicular basaltic trachyandesite in one of lava tubes (Duplex) that formed during the 2012–2013 eruption of the Tolbachik volcano, Kamchatka. This mineral is commonly associated with hematite, tenorite, halite, sylvite, and Ca-rich silicates (mainly, esseneite and Na-rich melilite) in high-temperature (800–1000 ◦C) reactionary zones (up to 100 µm) covering vesicular rocks and lava stalactites in the Duplex tube. The mineral relationships of this assemblage indicate the following crystallization sequence: Ca-rich silicates + hematite ! Cu-rich magnesioferrite ! tenorite ! chlorides. This formed due to the reaction of hot gases containing Cu, alkalis, and Cl with solidified lava rock. The composition of magnesioferrite varies strongly in CuO (5.8–17.3 wt %; cuprospinel end-member—15–47 mol %), whereas the contents of other oxides are minor, indicating the main isomorphic substitution is Mg2+ $ Cu2+. Compositions with maximal CuO content nominally belong to Mg-rich cuprospinel: (Cu0.48Mg0.41Mn0.09Zn0.02Ca0.02) 3+ (Fe 1.94Al0.03Ti0.02)O4. Increasing CuO content of the Duplex Cu-rich magnesioferrite is reflected in Raman spectra by moderate right shifting bands at ≈700–710 and 200–210 cm−1 and the appearance of an additional band at 596 cm−1. This supports the main isomorphic scheme and may indicate a degree of inversion in the spinel structure. Keywords: magnesioferrite; cuprospinel; hematite; tenorite; trachyandesite; lava tube; Tolbachik volcano; Kamchatka 1. Introduction Copper-rich spinels are well-documented in synthetic compounds, but rarely occur as minerals in the natural environment. Their origin is largely attributed to combustion processes or fumarole activity 3+ in young volcanoes. Cuprospinel, CuFe 2O4, was first described as a new mineral species from burnt dump from the Consolidated Rambler Mines Limited near Baie Verte, Newfoundland, Canada [1]. In this semi-anthropogenic system, cuprospinel is associated with Cu-rich magnesioferrite (13.9 wt % CuO) and hematite. This assemblage was formed as a result of a spontaneous ignition and burning of the mined copper–zinc ore. Cuprospinel, together with delafossite (CuFeO2), tenorite, and Fe-silicates, Minerals 2018, 8, 514; doi:10.3390/min8110514 www.mdpi.com/journal/minerals Minerals 2018, 8, 514 2 of 22 Minerals 2018, 8, x FOR PEER REVIEW 2 of 21 weredelafossite found as (CuFeO products2), oftenorite, oxidative and combustion Fe-silicates, of were copper found sulfides as products and related of oxidative phases (hematite, combustion quartz, of andcopper K-silicates), sulfides alongand related with anphases additional (hematite, silica quartz, flux foundand K-silicates), at the Olympic along with Dam an copper additional smelter silica [2 ]. Aflux new Cu-richfound at spinel, the Olympic thermaerogenite Dam copper (CuAl smelte2O4; IMAr [2]. 2018-021), A new cuprospinel,Cu-rich spinel, and thermaerogenite other Cu-bearing spinel-group(CuAl2O4; IMA minerals 2018-021), (usually cuprospinel, with >6 wt and % CuO:other gahnite,Cu-bearing spinel, spinel-group and magnesioferrite) minerals (usually were recently with discovered>6 wt % CuO: in the gahnite, Arsenatnaya spinel, fumarole,and magnesioferrite) which occurs were in recently the Second discovered scoria cone in the of Arsenatnaya the Northern Breakthroughfumarole, which of the occurs 1975–1976 in the Second Great Tolbachikscoria cone Fissure of the Eruption,Northern Breakthrough Tolbachik volcano, of the Kamchatka,1975–1976 RussiaGreat [ 3Tolbachik–5] and in Fissure the Western Eruption, paleo-fumarole Tolbachik volcan field ato, MountainKamchatka, 1004, Russia ancient [3–5] eruption and in the of Western Tolbachik (≈paleo-fumarole2000 years) [5]. field In thisat Mountain paper, we 1004, present ancient detailed eruption descriptions of Tolbachik of (≈ a2000 new years) locality [5]. forIn this Cu-bearing paper, magnesioferritewe present detailed within thedescriptions Tolbachik volcanicof a new system, locality where for itCu-bearing occurs as exhalationmagnesioferrite products within in basaltic the trachyandesitesTolbachik volcanic from thesystem, Duplex where lava it tubeoccurs of theas exhalation 2012–2013 products flank fissure in basaltic eruption. trachyandesites The findings offrom new Cu-richthe Duplex spinels lava provide tube of new the insights 2012–2013 into flank a new fiss Cu-dominanture eruption. clanThe withinfindings the of spinelnew Cu-rich supergroup spinels [6 ]. provide new insights into a new Cu-dominant clan within the spinel supergroup [6]. 2. Brief Data of the 2012–2013 Fissure Eruption of the Tolbachik Volcano 2. Brief Data of the 2012–2013 Fissure Eruption of the Tolbachik Volcano The 2012–2013 flank fissure eruption of the Tolbachik volcano in the Kamchatka Peninsula (Far East,The Russia) 2012–2013 lasted flank 9 months fissure anderuption produced of the 0.54Tolbachik km3 of volcano basaltic in trachyandesite the Kamchatka lava Peninsula that covered (Far a totalEast, areaRussia) of 36 lasted km2 with9 months a maximum and produced thickness 0.54 of km 703 mof [basaltic7] (Figure trachyandesite1). This eruption lava isthat considered covered a as onetotal of thearea most of 36 voluminous km2 with a maximum historical outpouringthickness of of70 basicm [7] lava(Figure in a1). subduction-related This eruption is considered environment. as Duringone of the the eruption,most voluminous the style historical of lava propagation outpouring of gradually basic lava changed in a subduction-related from channel-fed environment. ‘a’a flowsto tube-fedDuring pahoehoe the eruption, flows the [ 8style]. When of lava the propagation rate of magma gradually discharge changed declined from from channel-fed the initial ‘a’a 440 flows m3/s to to 3 severaltube-fed tens pahoehoe of m3/s inflows January [8]. When 2013, lavathe rate tubes of magma started formingdischarge via declined surface from solidification the initial (“roofing”) 440 m /s toof several tens of m3/s in January 2013, lava tubes started forming via surface solidification (“roofing”) the open lava channels (Figure2A). During the later stages of the eruption, the tube system extended of the open lava channels (Figure 2A). During the later stages of the eruption, the tube system downslope by complex branching to reach a total length of ≈4 km and included multiple interlacing extended downslope by complex branching to reach a total length of ≈4 km and included multiple tubes with average diameters ranging from 1 to 10 m. interlacing tubes with average diameters ranging from 1 to 10 m. FigureFigure 1. Sketch1. Sketch map map after after References References [8,9 ][8,9] showing showin theg distribution the distribution of the of 2012–2013 the 2012–2013 Tolbachik Tolbachik eruption lavaeruption fields, fissures,lava fields, vents, fissures, and thevents, location and the of location the Duplex of the lava Duplex tube segment lava tube (sampling segment (sampling site). The mapsite). is derivedThe map from is TERRA,derived ASTERfrom TERRA, (NASA, ASTER JPL), and (NASA, EO-1 ALIJPL), (NASA) and EO-1 satellite ALI image(NASA) interpretations satellite image and fieldinterpretations observations. and The field topographic observations. base The is a topogr DEM-derivedaphic base from is a SRTM DEM-derived X-band (DLR). from SRTM X-band (DLR). Minerals 2018, 8, 514 3 of 22 Minerals 2018, 8, x FOR PEER REVIEW 3 of 21 FigureFigure 2. 2. (A()A Gas-venting) Gas-venting skylight skylight in inthe the lava lava tube tube during during the Tolbachik the Tolbachik eruption eruption in 2012–2013. in 2012–2013. (B) Entrance(B) Entrance into intothe theDuplex Duplex lava lava tube tube after after the the 2012–2013 2012–2013 eruption, eruption, June June 2017. 2017. (C ()C Lava) Lava “stalactites” “stalactites” coveredcovered with with chlorides chlorides on on the the roof roof of of the the Duplex Duplex tube, tube, June June 2017. 2017. LavaLava flowing flowing through the tubetube systemsystem preservedpreserved temperatures temperatures and and viscosities viscosities close close to to those those in thein thesource source (1082 (1082◦C and °C(1 and−3) (1×−103)3 ×Pa 10·s)3 [8Pa],∙ buts) [8], experienced but experienced degassing, degassing, which was which frequently was observedfrequently as observedbursting bubblesas bursting at the bubbles lava surface. at the Gases lava released surface. from Gases the released lava leaked from upwards the lava through leaked the upwards fractured throughroof of the the
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