Properties of fluids during metasomatic alteration of metamorphic rocks under P-T conditions of the middle crust: an example from the Bolshie Keivy region, Belomorian-Lapland orogen, Fennoscandian shield

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Abstract

Properties of fluids under P–T conditions of the middle crust were studied with reference to the metasomatic alteration of metamorphic rocks (amphibolite facies) of the Bolshie Keivy nappe of the Keivy terrane of the Belomorian–Lapland collision orogen of the Fennoscandian shield. Properties of the fluids were studied in five selected types of rocks: metamorphic schists and gneisses with graphite, metasomatic quartz rocks with a high content of graphite, kyanite–quartz veins with wall-rock metasomatites, and metasomatic quartz-bearing kyanite rocks and anchimonomineral quartz veins. NaCl, CaCl2, CO2, N2, CH4, heavier hydrocarbons, and graphite were identified in the fluid inclusions using microthermometry and Raman spectroscopy. Using the method of multiequilibrium thermobarometry for mineral associations and the density of CO2 inclusions, a retrograde P–T path was calculated, which reflects the P–T exhumation history of the rocks. An explanation was proposed for the presence of water inclusions with NaCl of low salinity among inclusions of high salinity with NaCl and CaCl2. Comparison of data on the H2O activity (inferred from mineral equilibria) and salt content (data on fluid inclusions) with those of a model fluid (thermodynamic model of the H2O–NaCl–CaCl2–CO2 system) showed a good agreement between natural and model data. Natural and model data were synthesized to analyze variations in the phase state and chemical composition, fluid properties, including H2O activity, density, and salinity along the retrograde P–T trend.

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About the authors

S. А. Bushmin

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Author for correspondence.
Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

E. A. Vapnik

Ben-Gurion University of the Negev

Email: s.a.bushmin@ipgg.ru

Department of Geological and Environmental Sciences

Israel, Beer-Sheva

М. V. Ivanov

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

A. В. Kol’tsov

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

Y. М. Lebedeva

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

О. V. Aleksandrovich

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

Е. V. Savva

Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences

Email: s.a.bushmin@ipgg.ru
Russian Federation, St. Petersburg

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2. Fig. 1. Scheme of cover structures of the northern part of the Keivy Terrane (Bushmin et al., 2011a), with modifications. 1 - granites, granite-gneisses and gneisses of the Kola Craton, 2 - anorthosites, 3 - alkaline granites, 4 - garnet-biotite and garnet-amphibole-biotite gneisses with amphibolite bodies, alkaline metasomatites, 5 - high-alumina metamorphic and metasomatic rocks with amphibolite and plagioclasite bodies (meta-anorthosites), 6 - tectonic boundaries along thrusts, 7 - color symbols indicate sampling locations of different rock types. Type 1: a - metamorphic gneisses and schists with graphite; b - amphibolites; type 2: c - metasomatic quartz rocks with increased graphite content; type 3: g – kyanite-quartz veins with near-vein metasomatites; type 4: d – metasomatic kyanite rocks; type 5: e – anchimonomineral quartz veins. The inset shows the location of the study area.

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3. Fig. 2. Photos of samples of different rock types and salt content in brine inclusions. Type 1: (a) and (b) – gneisses and schists with graphite, Bt1 and Bt2 – early and late generation biotite, (c) – salt content in gneisses and schists (yellow triangles – inclusions with NaCl only). Type 2: metasomatic Qz rocks with increased graphite content, (d) – black banded graphite-rich Ky-Qz blastomylonite, (d) – enlarged section of blastomylonite, (e) – black-gray massive graphite-rich quartz metasomatite, (g) – salt content in metasomatic Qz rocks rich in Gt (yellow circles – inclusions with NaCl only).

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4. Fig. 3. Photos of inclusions in the studied rock types. BR – brine, H – halite, L – liquid phase, V – gas phase. Type 1: (a) – p-inclusion of CO2 with Gt and ps-inclusions of brine, sample B878-4; type 2: (b) – ps-inclusions of brine with halite and ps-inclusions of CO2, sample E3-1a; (c) and (d) – ps-inclusions of brine with halite ±CO2 and ps-inclusions of CO2, sample E1-3b; (d) – ps-inclusions of brine with halite and ps-inclusions of CO2, sample E5-4; (e) – ps-inclusions of brine with halite, CO2, Cal and ps-inclusions of CO2, sample E5-4; (g) – ps-inclusions of CH4 with CnHm and H2, sample E5-4; (z) – p-inclusions of CH4 with CnHm and Gt, sample K8-a; (i) – p-inclusion of C2H6 with CnHm and CH4, sample K8-d.

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5. Fig. 4. Photos of samples of different rock types and salt content in brine inclusions. Type 3: (a) and (b) – Ky-Qz vein with wall-vein metasomatite and salt content (yellow circles – inclusions with NaCl only). Type 4: (c) and (d) – metasomatic Ky rocks and salt content (yellow circles – inclusions with NaCl only). Type 5: (d) – anchimonomineral Qz vein, (e) – wall-vein zone ~0–5 cm, (g) – salt content in Qz vein (yellow circles – inclusions with NaCl only).

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6. Fig. 5. Photos of inclusions in the studied rock types. BR – brine, H – halite, L – liquid phase, V – gas phase. Type 3: (a) – association of ps-inclusions of brine, brine with H and Cal, CO2 inclusions in the Ky-Qz vein, sample B880-6a; (b) – ps-inclusion of CH4 among CO2 inclusions in the wall-vein metasomatite, sample B880-6b; (c) – ps-inclusion of CO2 in the wall-vein metasomatite, sample B884-1v. Type 4: (d) – ps-inclusions of brine with H, sample B901-6; (e) – p- and ps-inclusions of CO2, sample B901-6. Type 5: (e) – association of ps-inclusions of brine and CO2 inclusions, next to it a group of p-inclusions of CO2, sample B926-3.

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7. Fig. 6. Р-Т conditions of formation of the studied metamorphic and metasomatic rocks of the gneiss-schist sequence of the Bol'shiye Keivy tectonic nappe. Legend of rock types as in Fig. 1. Metamorphic facies: GS – greenschist, AM – amphibolite, GR – granulite, EC – eclogite (Bushmin, Glebovitsky, 2016). Dashed red line – generalized Р-Т trend of retrograde change in rock formation conditions. 1 – area of ​​Р-Т parameters (Р ~ 7–6.5 kbar, Т ~ 525–500°C) of Ky-Qz veins with wall-vein metasomatites (type 3) according to (Bushmin et al., 2011б); 2 – decompression area (6.8–3.4 kbar at ~500°C) according to microthermometry data of CO2 inclusions (Table 3) in Ky-Qz veins with near-vein metasomatites (type 3), Qz-Ky veins, veinlets and veinlet zones (type 4) and anchimonomineral Qz veins (type 5).

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8. Fig. 7. Examples of the results of calculating the P-T parameters by the avPT method for typical samples of the studied rock types. (a, b) – metamorphic gneiss and schist; (c, d, d) – metasomatic quartz rocks with increased graphite content; (e) – metasomatic Ky quartzite.

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9. Fig. 8. Section of the phase diagram of the H2O-NaCl-CaCl2-CO2 fluid system through the H2O-CO2-salt ratio vertices. ysalt – mole fractions of total salinity in the quaternary system, yCO2 – mole fractions of CO2 in the quaternary system. Solvi and phase fields at T = 560°C, P = 7.5 kbar and xr = 0.75 (ratio of the mole fraction of NaCl to the total mole fraction of salt). Numbers designate regions (fields) of different phase composition: 1 – homogeneous fluid, 2 – two coexisting fluid phases, 3 – two fluid phases coexisting with a solid phase of NaCl (the boundaries are designated for T = 560°C, P = 7.5 kbar, xr = 0.75 – bold green lines). Thin black lines connect solvus points with the same water activities. a – xsalt = 0.299, b – xsalt = 0.143, c – xsalt = 0.221 – points of maximum, minimum and average salinity of water-salt fluid in samples E6, E5, K8.

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10. Fig. 9. Relative presence of gas inclusions (CO2 and CH4) and brines (H2O, salts taking into account the mass % of salts) in quartz in the studied rock types: (a) type-1, (b) type-2, (c) type-3, (d) type-4, (e) type-5.

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11. Fig. 10. Inclusions in type-2 rocks. Gray circles are the water-salt compositions of the studied fluid inclusions in samples E3 (a) and E5, E6, K8 (b). Colored symbols are the compositions of the fluids of the initial inclusions and the corresponding compositions of the layered fluids. The points corresponding to the compositions of the fluids of the initial inclusions are additionally marked with a + sign of the same color. Compositions of the model fluids of the initial inclusions (y are the mole fractions of the components in the quaternary system H2O-NaCl-CaCl2-CO2), P-T parameters at which phase separation occurred: 1. yH2O = 0.719, yCO2 = 0.197, yNaCl = 0.049, yCaCl2 = 0.035, T = 320°C, P = 2 kbar; 2. yH2O = 0.712, yCO2 = 0.205, yNaCl = 0.043, yCaCl2 = 0.040, T = 320°C, P = 2 kbar; 3. yH2O = 0.736, yCO2 = 0.184, yNaCl = 0.038, yCaCl2 = 0.042, T = 320°C, P = 2 kbar; 4. yH2O = 0.653, yCO2 = 0.237, yNaCl = 0.090, yCaCl2 = 0.020, T = 500°C, P = 4 kbar; 5. yH2O = 0.614, yCO2 = 0.222, yNaCl = 0.140, yCaCl2 = 0.024, T = 500°C, P = 4.3 kbar; 6. yH2O = 0.522, yCO2 = 0.391, yNaCl = 0.072, yCaCl2 = 0.016, T = 470°C, P = 2 kbar.

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12. Fig. 11. Inclusions in type-4 rocks. Composition of the model fluid of the original inclusion: yH2O = 0.734, yCO2 = 0.211, yNaCl = 0.028, yCaCl2 = 0.028. T = 390°C, P = 1.4 kbar. See also the caption to Fig. 10.

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13. Fig. 12. Phase diagrams of fluids along the generalized P-T trend of retrograde change in the formation conditions of the studied types of metamorphic and metasomatic rocks of the Bol'shiye Keivy nappe. (a) – type-1, (b) – type-2, (c) – type-3, (d) – type-4, (e) – dashed red line – generalized P-T trend. Bold blue lines – solvuses. For phase field designations, see the caption to Fig. 8. Unfilled circles are critical points of solvuses, at which water activity reaches the maximum value possible in the region of heterogeneous fluid. Red circles are maximum mole fractions of salt in the water-salt part of the fluid for each of the rock types. The dotted red line in Figure (a) is the solvus for P-T conditions of type-2 rocks. aH2O is the water activity, ρ is the density of fluid phases (g/cm3).

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