Volatile Contents during the Formation of Olivinite and Olivine-Monticellite Rocks of the Krestovskaya Alkaline-Ultrabasic Carbonatite Intrusion, Polar Siberia: Pyrolysis-Free Gas Chromatography-Mass Spectrometry Data

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The parental larnite-normative alkaline ultramafic melt consistently forming olivinite and olivine-monticellite rocks of the Krestovskaya alkaline-ultrabasic carbonatite intrusion is enriched with hydrocarbons (HC) and their derivatives, nitrogenated, chlorinated, fluorinated, sulfonated compounds, as well as H2O and CO2 according to pyrolysis-free gas chromatography-mass spectrometry data (GC-MS). The aliphatic, cyclic, oxygenated compounds, and very few heterocyclic compounds are determined among the hydrocarbons. During the crystallization of olivine in olivinites, fluids are enriched in hydrocarbons (59.30 rel. %), excluding nitrogenated, chlorinated, and sulfonated derivatives and including predominant amount of oxygenated compounds (52.17 rel. %) and subordinate amount of aliphatic and cyclic compounds (6.70 rel. %). During the crystallization of perovskite in olivine-monticellite rocks, the amount of oxygenated hydrocarbons slightly decreases (34.77 rel. %) and aliphatic and cyclic compounds increases up to 10.55 rel. %. The crystallization of monticellite is accompanied by the predominance of aliphatic and cyclic hydrocarbons (59.67 rel.%) and subordinate amounts of oxygenated hydrocarbons (29.35 rel. %). The fact that the calculated H/(O + H) ratio is 0.78 and 0.77 for fluids in olivine and perovskite, respectively indicates the reducing conditions of crystallization of these minerals. On the stage of olivine crystallization of olivinite, the fluids also contain 4.1 rel. % of nitrogenated, 4.58 rel. % of sulfonated, 0.19 rel. % chlorinated, 0.12 rel. % fluorinated hydrocarbons, 0.49 rel. % CO2, and 31.17 rel. % H2O. The crystallization of perovskite in olivine-monticellite rocks is accompanied by further accumulation of nitrogenated compounds up to 8.95 rel. %, sulfonated (9.53 rel. %) and chlorinated (11.33 rel. %) hydrocarbons, and 16.48 rel. % CO2. In this stage the content of H2O in the fluids decreases to 7.66 rel. % due to its binding to cations and Al-Si-radicals of the melt into hydroxyl-bearing compounds. At the final stage of crystallization of perovskite and initial monticellite, when fluids are saturated by critical amounts of chlorinated, nitrogenated and sulfonated compounds and CO2, they become to dissolve in the melt and react with it: most of the considered fluids, together with Ca and alkalis of the melt, form carbonate-salt compounds and the melt became silicate-salt composition. According to GC-MS analysis data, residual fluid phase of monticellite-hosted inclusions are characterized by only 2.29 rel. % nitrogenated and 1.11 rel. % sulfonated, 0.32 rel. % chlorinated, and 0.35 rel. % fluorinated hydrocarbons, 0.04 rel. % CO2 and 6.15 rel. % H2O with an increase in hydrocarbons up to 89.63 rel. %. During the crystallization of monticellite, silicate-salt immiscibility occurred, followed by spatial separation of the silicate and salt fractions.

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L. Panina

Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences

编辑信件的主要联系方式.
Email: panina@igm.nsc.ru
俄罗斯联邦, Novosibirsk

E. Rokosova

Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences

Email: rokosovae@igm.nsc.ru
俄罗斯联邦, Novosibirsk

A. Isakova

Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences; Novosibirsk State University

Email: atnikolaeva@igm.nsc.ru
俄罗斯联邦, Novosibirsk; Novosibirsk

A. Tomilenko

Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences

Email: panina@igm.nsc.ru
俄罗斯联邦, Novosibirsk

T. Bul'bak

Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences

Email: panina@igm.nsc.ru
俄罗斯联邦, Novosibirsk

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2. Fig. 1. Scheme of the geological structure of the Krestovskaya volcano-plutonic structure (Sazonov et al., 2001). 1 - modern alluvial deposits; 2 - undifferentiated Quaternary deposits; 3 - effusive sequence of melanephelinites; 4 - clastolaves of melanephelinites; 5, 6 - dikes: 5 - alkaline microsyenites; 6 - trachybasalts, trachydolerites, plagioclase porphyrites and picrites; 7 - nested dikes (microsyenites, trachybasalts, alkaline picrites); 8 - melilitholites; 9 - olivinites, wehrlites and pyroxenites; 10 - monticellitelites and olivine-monticellite rocks; 11 – facies of fenites and fenitized rocks: a – perovskite-aegirine-augite; b – titanite-biotite-aegirine-augite; 12 – perovskite fenites: a – uniformly fine-grained, b – blastoporphyritic; 13 – biotite-bearing fenitized rocks; 14 – injection melilitolite-ultramafics, skarnified and recrystallized rocks of the contact zone of melilitolite bodies; 15 – geological boundaries; 16 – supposed faults. The inset shows the geographical position of the Maimecha-Kotui province: G – Guli pluton; K – Krestovskaya intrusion.

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3. Fig. 2. Inclusions in olivine from olivinites: (a) location of primary melt inclusions; (b) location of secondary fluid inclusions along a crack; (c, d) primary melt inclusions (Panina et al., 2018); (e) secondary fluid inclusions. (a, b, d) transmitted light image, (c, d) reflected electron image. Grt – garnet, Ks – kalsilite, Mtc – monticellite, Ol – olivine, Prv – perovskite, Phl – phlogopite, Mag – magnetite.

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4. Fig. 3. Inclusions in minerals of olivine-monticellite rocks of the Krestovskaya intrusion: (a) location of primary melt inclusions in the center of a perovskite grain; (b, c) primary melt inclusions in perovskite (Panina et al., 2018, 2023); (d) location of primary melt inclusions in a monticellite grain; (e) location of secondary fluid inclusions along a crack in a monticellite grain; (e, g) primary melt inclusions in monticellite (Panina et al., 2023); (h) secondary fluid inclusions in monticellite. (d, e, f, g, h) – image in transmitted light; (a, b, c) – image in reflected electrons. Ap – apatite, Cal – calcite, Cpx – clinopyroxene, hGrt – hydrogarnet, Ks – calcilite, Mag – magnetite, Mtc – monticellite, Nph – nepheline, Pct – pectolite, Prv – perovskite, Phl – phlogopite, cc – salt aggregate, g. – gas phase, r.f. – ore phase.

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5. Fig. 4. Primary melt inclusion in olivine of olivinites and KR spectra of its main phases. Mtc – monticellite, Ol – olivine, Phl – phlogopite, Mag – magnetite, Gas phase – gas phase.

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6. Fig. 5. Primary melt inclusion in monticellite of olivine-monticellite rock and KR spectra of its main phases. Cal – calcite, Cpx – clinopyroxene, Mtc – monticellite, Gas phase – gas phase.

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7. Fig. 6. Relative contents of hydrocarbons, carbon dioxide, water, and nitrogen-containing, sulfur-containing, and halogen-containing compounds in the gas phase of inclusions from olivines of olivinites (a), perovskites (b), and monticellites (c) of the olivine-monticellite rock of the Krestovskaya intrusion, obtained using GC-MS.

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8. Fig. 7. Histogram of distribution of relative contents of: (a) aliphatic, cyclic, oxygen-containing hydrocarbons (HC); (b) “light” (C1–C4), “medium” (C5–C12), “heavy” (C13–C18) paraffins; (c) alcohols and ethers, aldehydes, ketones, and carboxylic acids in oxygen-containing HC compounds; (g) the sums of hydrocarbons, CO2, H2O, sulfur-containing, nitrogen-containing and chlorine-containing compounds in olivine of olivinites, perovskite and monticellite of olivine-monticellite rocks.

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9. Results of GC-MS analysis of the gas phase extracted during impact destruction of olivine from olivinite of the Krestovsky massif (species diversity of 285 components)
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10. Results of GC-MS analysis of the gas phase extracted during impact destruction of perovskite from olivine-monticellite rocks of the Krestovskaya intrusion (species diversity of 256 components)
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11. Results of GC-MS analysis of the gas phase extracted during impact destruction of monticellite from olivine-monticellite rocks of the Krestovskaya intrusion (species diversity of 282 components)
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