Rocks of the Ary-Bulak ongonite massif: relationship between geochemical features, mineral-phase assembleges, and formation processes

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Abstract

The paper reports the study of geochemistry, mineral-phase assemblages of rocks of the Ary-Bulak ongonite massif, compositions of major, minor and accessory minerals (quartz, feldspars, topaz, zinnwaldite, prosopite, rare Ca–Al-fluorides, W-ixiolite, columbite, zircon, cassiterite, and fluocerite), fluoride–calcium (F-Ca) phase, and fluorite formed from it. The rock-forming minerals of porphyritic ongonites are quartz, albite and sanidine, and minor minerals are topaz and zinnwaldite. The ongonitic matrix is composed of a quartz–sanidine–albite assemblage with micron-sized needle-shaped topaz crystals. In transitional porphyritic rocks and in the endocontact aphyric zone, the interstices between matrix minerals are filled with a F-Ca phase formed from a F-Ca (fluoritic) stoichiometric melt. Fluoride–silicate liquid immiscibility in ongonitic magma and fluid-magmatic processes led to the redistribution of REE, Y, and many trace elements between melts, fluids, minerals and a contrasting change in mineral-phase assemblages in the rocks. This is associated with the appearance of M-type (T1 La–Nd, T4 Er–Lu) and W-type (T3 Gd–Ho) tetrad effects in the chondrite-normalized REE patterns of rocks. Degassing of magmatic fluids through the endocontact aphyric zone was accompanied by the crystallization of Sr-bearing prosopite and hydrous Ca–Al-fluorides. Aphyric rocks, compared to porphyritic ongonites and porphyritic transitional rocks, are enriched in H2O, Sr, Ba, Rb, Sn, W, Ta, Be, Zr, Hf, Sb, As, Sc, but contain less Li, Pb, Zn, Y and REE. During the effect of magmatic fluids on rocks enriched in Ca and F, especially in the endocontact aphyric zone, albite was partially or completely replaced by the F-Ca phase and kaolinite, and the F-Ca phase recrystallized into aggregates of micron-sized grains of stoichiometric fluorite without trace elements. Rb-Cs mica also crystallized in the rim of zinnwaldite laths, the zones of which maximally enriched in rubidium with the cation relation Rb > K > Cs may be a new mineral. The geochemistry of the rocks, the features of their mineral-phase assemblages, the compositional evolution of the minerals and the F-Ca phase are a consequence of the formation of the Ary-Bulak massif from ongonitic magma during a fluid-magmatic process complicated by fluoride–silicate liquid immiscibility with the participation of fluoritic and other fluoride melts, as well as magmatic fluids of P-Q and the first types.

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About the authors

I. S. Peretyazhko

A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: pgmigor@mail.ru
Russian Federation, Irkutsk

E. A. Savina

A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences

Email: pgmigor@mail.ru
Russian Federation, Irkutsk

A. S. Dmitrieva

A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences

Email: pgmigor@mail.ru
Russian Federation, Irkutsk

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2. Fig. 1. Geological maps-schemes of the Ary-Bulak massif according to literary data. (a) Scheme by B. A. Gaivoronsky, published in (Kovalenko, Kovalenko, 1976). 1 – sedimentary and volcanic rocks of the Ust-Borzinskaya suite, 2 – basaltoids, 3 – aphyric endocontact ongonites, 4 – porphyry ongonites. (b) Vertical section of the massif, according to (Troshin et al., 1983). 1 – metaeffusives, 2 – andesites, andesite-basalts, 3 – ongonites, 4 – Quaternary deposits, 5 – wells. (c) Map, according to (Antipin et al., 2009). 1 – Quaternary deposits, 2 – porphyritic ongonites, 3 – “crystallized ongonites, with Ca-F glass”, 4 – aphyric ongonites, fine-grained and glassy, ​​5 – basalts, andesite-basalts, 6 – limestones, 7 – shales. Note that the rocks of the Ary-Bulak massif, according to our data, do not contain silicate or any fluoride glass.

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3. Fig. 2. Geological map of the Ary-Bulak massif. Constructed taking into account the data of drilling and geophysical works carried out by geological parties – Chesucheyskaya in 1964–1965 and Leontyevskaya in 1967–1969 (materials provided by geologist B.A. Gaivoronsky).

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4. Fig. 3. Rocks of the massif: (a) – porphyritic ongonite with crystals of smoky quartz, topaz and sanidine, sample ARB-28; (b) – transitional porphyry rock, sample ARB-26. (c) – aphyric rock, sample ARB-19; (d–f) – microstructural features in thin sections (polarizers are half-crossed): (d) – porphyritic ongonite, sample ARB-34; (d) – transitional porphyry rock, sample ARB-190; (e) – aphyric rock, sample ARB-184. Length of scale bar in (a–c) – 10 mm, in (d–f) – 1 mm. Qz – quartz, Tpz – topaz, Ab – albite, Sa – sanidine, Psp – prosopite, F-Ca – calcium fluoride phase.

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5. Fig. 4. Ratios of K2O, Na2O, CaO, F and SiO2 in the rocks of the massif.

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6. Fig. 5. A/CNK–A/NK diagram and the relationships between SiO2 and K2O, Al2O3, Na2O, (FeO + Fe2O3), H2O, TiO2, CO2 in the rocks of the massif. For legend, see Fig. 4.

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7. Fig. 6. Relationships between SiO2 (wt.%) and Li, Rb, Cs, Ba, Sr, Zr, Ta, Nb, W, Sn, Zn, Pb (ppm) in the rocks of the massif. For legend, see Fig. 4. Concentrations of W, Sn, Zn, Pb – according to quantitative spectral analysis, other elements – according to ICP-MS.

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8. Fig. 7. Multi-element distributions of massif rocks normalized to the primitive mantle. Concentrations of elements in the primitive mantle according to (McDonough, Sun, 1995).

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9. Fig. 8. Chondrite-normalized REE distributions of the massif rocks. Element concentrations in chondrite C1 after (McDonough, Sun, 1995). Lines with signs show the REE spectra for average rock compositions. Samples ARB-24 and ARB-105 are characterized by a negative cerium anomaly. T1, T3, and T4 are REE tetrads as a consequence of fluoride-silicate immiscibility for porphyry ongonites (a), interaction of magmatic fluids with transitional porphyry rocks (b), and the aphyric zone of the massif (c).

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10. Fig. 9. Mineral associations of rocks in thin sections (polarizers are crossed). (a) – intergrowth of albite and sanidine crystals, sample ARB-357. (b) – ongonite matrix, sample ARB-34. (c) – topaz crystal with a rim containing melt and fluid inclusions, sample ARB-34. (d) – zonal zinnwaldite, sample ARB-146. (d) – prosopite and topaz in aphyric rock, sample ARB-19. (e) – aphyric rock matrix, sample ARB-54. (g) – albite phenocrysts (contours shown) are completely replaced by the F-Ca phase and/or kaolinite, sample ARB-343. (z) – calcite aggregate in ongonite matrix, sample ARB-142. Scale bar length is 200 μm. Ab – albite, Sa – sanidine, Qz – quartz, Tpz – topaz, Mica – zinnwaldite, Psp – prosopite, F-Ca – calcium fluoride phase, Kln – kaolinite, Cal – calcite.

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11. Fig. 10. Feldspars in rocks: (a) – case albite crystals with a rim of sanidine in a transitional porphyry rock, sample ARB-106; (b) – albite crystal in sanidine is partially replaced by the F-Ca phase in an aphyric rock, sample ARB-184; (c) – case albite crystal is completely replaced by the F-Ca phase and kaolinite in an aphyric rock, sample ARB-4; (d) – sanidine crystal with albite inclusions, some of which are replaced by the F-Ca phase in an aphyric rock, sample ARB-182. In the matrix of aphyric rocks (c and d), the F-Ca phase contains acicular inclusions of sanidine of micron sizes. Length of scale bar – 100 μm. See Fig. for legend. 9. BSE images.

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12. Rice. 11. Compositions of feldspars in the diagram anorthite (An)–orthoclase (Or)–albite (Ab). Minals: Sa – sanidine, Ant – anorthoclase, Olg – oligoclase.

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13. Fig. 12. Fluoride crystalline phases in aphyric rocks. (a) – prosopite phenocrysts, sample ARB-325; (b) – prosopite and sanidine intergrowth, sample ARB-19; (c) – fluorite crystals in the F-Ca phase, sample ARB-106; (d) – veinlet in sample ARB-4 with insets: (d) – gearxutite in the F-Ca phase, (e) – undiagnosed calcium aluminofluoride, the composition of which is compared with karlhintzeite. The length of the scale bar in (a, b, d) is 100 μm, in (c, d, e) – 10 μm. Fl – fluorite, Gak – gearxutite, Chz? – undiagnosed calcium aluminofluoride, other designations see in Fig. 9. (a–b) – photographs of thin sections, polarizers are crossed, (c–e) – BSE images.

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14. Fig. 13. Topaz in rocks: (a) – acicular crystals in the matrix, sample ARB-34; (b) – crystal with mineral inclusions, sample ARB-371; (c) – crystal with inclusions of albite, zinnwaldite and wolframoixiolite, sample ARB-106; (d) – inclusions of acicular crystals of wolframoixiolite, sample ARB-34. The scale bar in (a, b, d) is 50 µm, in (c) – 1 mm. W-Ix – wolframoixiolite, other designations see in Fig. 9; (a, c) – BSE images; (b, d) – photographs of thin sections in transmitted light.

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15. Fig. 14. Zinnwaldite in rocks: (a) – with numerous inclusions, sample ARB-34 and (b) – ARB-106; (c) – with a less ferruginous rim, sample ARB-370; (d) – with an Rb-Cs rim and an inclusion of columbite-(Mn), sample ARB-4. The scale bar is 50 μm. Clb – columbite-(Mn), Zrn – zircon, other designations see Fig. 9. BSE images.

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16. Fig. 15. Relationship between K, Rb and Cs in Rb-Cs mica from the rim of zinnwaldite laths in aphyric rock, sample ARB-4.

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17. Fig. 16. Compositions of calcium aluminofluorides in aphyric rocks (samples ARB-4, ARB-19, ARB-176 and ARB-182) on the Ca–F–Al diagram.

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18. Fig. 17. Accessory minerals: (a) – columbite-(Mn) and wolframoixiolite in zinnwaldite, sample ARB-136; (b) – needle-shaped crystals of wolframoixiolite in topaz, sample ARB-146; (c) – xenotime in zinnwaldite, sample ARB-106; (d) – zircon and fluocerite-(Ce) in transitional porphyry rock, sample ARB-353; (d) – cassiterite in transitional rock, sample ARB-131. Length of scale bar in (a–d) – 100 µm, in (d) – 20 µm. Xtm – xenotime, Fcrt-Ce – fluocerite-(Ce), Cst – cassiterite, other designations see Fig. 9, 13 and 14. (a–c) photographs of thin sections, transmitted light (a) polarizers are crossed (b, c), (d, d) – BSE images.

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