Minerals of the Tochilinite-Ferrotochilinite Series from Rocks of the Urals and Trans-Urals: Mineral Associations, Chemical Composition, Genesis

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Abstract

The paper presents the results of studying the scarce iron–magnesium sulfide-hydroxides of the tochilinite-ferrotochilinite series with the ideal formula 6FeS·5Mg(OH)2. These minerals are formed during serpentinization of ultrabasites of different nature and were described in peridotites of the Kempirsai, Khabarny, Kytlym and Uktus massifs in the Urals and the Verkhne-Iusskaya area of the Shaim petroleum region of Western Siberia. The aim of this work is to examine the poorly studied chemical composition of tochilinite, to determine its mineral associations and conditions of formation. The minerals were analyzed by optical and electron scanning microscopy, Raman and IR spectroscopy. Based on the magnesium number (ХMg), the minerals could be divided into tochilinite and ferrotochilinite. High-Mg minerals (ХMg = 0.73–0.79) are found in the Uktus massif and in the Verkhne-Iusskaya area, and low-Mg varieties (ХMg = 0.15–0.38) occur in the Khabarny and Kytlym massifs. The presence of mixed-layer phases represented by the alternation of nano-scale layers of tochilinite or ferrotochilinite with serpentine is assumed. The chromium-bearing varieties of tochilinite are noted. Mechanisms and chemical reactions leading to the formation of tochilinites during the low-temperature transformation of peridotite in the presence of water are discussed. In most cases, this is the interaction of metamorphic water with magmatic sulfides during the serpentinization of peridotite, or the influence of sedimentary or another waters containing dissolved sulfur on them. It is concluded that tochilinite served as a sulfur absorbent during early reticulate serpentinization of ultramafic rocks. Tochilinite could be used as a promising geothermometer for low-temperature ultramafic mineral assemblages.

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About the authors

S. V. Pribavkin

A.N. Zavaritsky Institute of Geology and Geochemistry, UB RAS

Author for correspondence.
Email: pribavkin@igg.uran.ru
Russian Federation, Yekaterinburg

E. V. Pushkarev

A.N. Zavaritsky Institute of Geology and Geochemistry, UB RAS

Email: pribavkin@igg.uran.ru
Russian Federation, Yekaterinburg

I. S. Chashchukhin

A.N. Zavaritsky Institute of Geology and Geochemistry, UB RAS

Email: pribavkin@igg.uran.ru
Russian Federation, Yekaterinburg

Yu. V. Erokhin

A.N. Zavaritsky Institute of Geology and Geochemistry, UB RAS

Email: pribavkin@igg.uran.ru
Russian Federation, Yekaterinburg

A. V. Korovko

A.N. Zavaritsky Institute of Geology and Geochemistry, UB RAS

Email: pribavkin@igg.uran.ru
Russian Federation, Yekaterinburg

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2. Fig. 1. Positions of tochilinite finds on the tectonic scheme of the Urals. EEP – East European Platform, WSP – West Siberian Plate, I–V – structural megazones of the Urals (I – West Ural, II – Central Ural, III – Tagil-Magnitogorsk, IV – East Ural, V – Trans-Ural). Ultramafic massifs are shown in black, granitoids – in pink. Asterisks indicate the locations of tochilinite finds: Verkhne-Iusskaya area (1), Kytlymsky (2), Bazhenovsky (3), Uktussky (4), Ufaleysky (5), Dzhetygarinsky (6), Khabarninsky (7), Kempirsaysky (8) massifs.

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3. Fig. 2. Backscattered electron (BSE) micrographs of tochilinite.

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4. Fig. 3. IR spectrum (a–c) and Raman spectra of samples 8003, 465/893, and M-920 (d). (a) – micrograph of sample 8003 with a rectangular area in the center of the image where the IR spectra were recorded. (b, c) – IR spectra in the range of 500–2000 and 3000–4800 cm−1. (d) – Raman spectra of the samples in comparison with the “reference” spectrum of tochilinite presented in RRUFF (RRUFF ID: R060887). The spectrum of sample 465/893 includes characteristic modes of matrix serpentine (shown with asterisks).

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5. Fig. 4. Diagrams of Mg–Fe ratios in the brucite-like layer of tochilinite samples (a, c, d) and ratios of normative Thi, Srp in the composition of mineral mixtures (b). 1 – Verkhne-Iusskaya area (sample 8003), 2 – Kytlymsky massif (sample PS-54), 3 – Kytlymsky massif (sample M-924), 4 – Uktussky massif (sample PS-548), 5 – Khabarninsky massif (samples 465/893, 465/940), 6 – Kempirsaisky massif (well 8697), 7 – natural tochilinite (Harris, Vaughan, 1972; Jambor, 1976; Muramatsu, Nambu, 1980; Matsubara, Kato, 1992; Zolensky, Mackinnon, 1986; Beard, 2001; Encheva et al., 2016; Organova et al., 1971; Chashchukhin and others, 1990; Varlakov, 1995; Aleksandrov, Senin, 2005; Pekov et al., 2012), 8 – tochilinite from meteorites (Tomeoka et al., 1989; Palmer, Lauretta, 2011; Haack et al., 2012; Tonui et al., 2014; Hewins et al., 2014), 9 – synthetic tochilinite (Peng, Jing 2014; Peng et al., 2007; Vacher et al., 2019; Bolney et al., 2022). The selection of tochilinite compositions presented in diagram (a) corresponds to Table 1.

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6. Fig. 5. Diagrams of element ratios in tochilinite samples (wt. %). 1 – Verkhne-Iusskaya area (sample 8003), 2 – Kytlymsky massif (sample PS-54), 3 – Kytlymsky massif (sample M-924), 4 – Uktussky massif (sample PS-548), 5 – Khabarninsky massif (samples 465/893, 465/940), 6 – Kempirsaysky massif (well 8697). See mineral symbols in Fig. 2. Arrows show trends in compositional changes in tochilinite mixtures with serpentine, cronstedtite, pyrrhotite, and magnetite. Compositional regions of the latter are also shown in the diagrams.

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7. Fig. 6. Composition–paragenesis diagrams (at. %) in the presence of H₂O, CO₂, H₂S. Adr – andradite, Amk – amakinite Fe(OH)2, Mag – magnetite, Cal – calcite, Chl – chlorite-like phyllosilicate (highlighted by an open circle due to incomplete correspondence of the composition to the components indicated in the diagram), Cro – cronstedtite, Dol – dolomite, Hmgs – hydromagnesite, Kam – kamacite, Pya – pyroaurite, Pyh – pyrrhotite, Sd – siderite, Srp – serpentine, Thi – tochilinite. Solid conodes show parageneses in the magnesian system, dotted ones – in the ferruginous system.

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8. Fig. 7. Magnesium content (nMg) in synthetic tochilinite and tochilinite-like phases as a function of temperature (a) and the dependence of magnesia (XMg) on ​​temperature for tochilinite and brucite (b).

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