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Carbon Sources and the Graphitization of Carbonaceous Matter in Precambrian Rocks of the Keivy Terrane (Kola Peninsula, Russia)

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Carbon Sources and the Graphitization of Carbonaceous Matter in Precambrian Rocks of the Keivy Terrane (Kola Peninsula, Russia) minerals Article Carbon Sources and the Graphitization of Carbonaceous Matter in Precambrian Rocks of the Keivy Terrane (Kola Peninsula, Russia) Ekaterina Fomina 1,* , Evgeniy Kozlov 1 , Kirill Lokhov 2, Olga Lokhova 3 and Vladimir Bocharov 4 1 Geological Institute, Kola Science Centre, Russian Academy of Sciences, 14, Fersmana Street, 184209 Apatity, Russia; [email protected] 2 Institute of Earth Sciences, Saint-Petersburg State University, 7/9, Universitetskaya Emb., 199034 St. Petersburg, Russia; [email protected] 3 Institute for the History of Material Culture, Russian Academy of Sciences, 18, Dvortsovaya Emb., 191186 St.-Petersburg, Russia; [email protected] 4 Resource Center for Geo-Environmental Research and Modeling (GEOMODEL), Saint-Petersburg State University, 1, Ulyanovskaya Street, 198504 St. Petersburg, Russia; [email protected] * Correspondence: [email protected]; Tel.: +7-921-276-2996 Received: 15 December 2018; Accepted: 3 February 2019; Published: 8 February 2019 Abstract: The Precambrian rocks of the Keivy Terrane reveal five types of carbonaceous matter (CM): Fine-grained, flaky, nest, vein, and spherulitic. These types differ in their distribution character, carbon isotope composition, and graphitization temperatures calculated by the Raman spectra of carbonaceous material (RSCM) geothermometry. Supracrustal rocks of the Keivy Terrane 13 contain extremely isotopically light (δ CPDB = –43 ± 3‰) carbon. Presumably, its source was a methane–aqueous fluid. According to temperature calculations, this carbon matter and the host strata underwent at least two stages of metamorphism in the west of the Keivy Terrane and one stage in 13 the east. The CM isotope signatures of several samples of kyanite schists (δ CPDB = –33 ± 5‰) are close to those of oils and oil source rocks, and they indicate an additional carbon reservoir. Thus, in 13 the Keivy territory, an oil-and-gas bearing basin has existed. Heavy carbon (δ CPDB = −8 ± 3‰) precipitated from an aqueous CO2-rich fluid is derived from either the lower crust or the mantle. This fluid probably migrated from the Keivy alkaline granites into the surrounding rocks previously enriched with “methanogenic” carbon. Keywords: graphitization; carbon isotopes; RSCM geothermometry; polyphase metamorphism; alkaline granites; Precambrian; Kola Peninsula; graphite 1. Introduction The Keivy Terrane of the Archean Kola Province, located in the northeast of the Baltic Shield, is a unique object for studying carbonaceous matter (CM). Different morphologies of CM are present in variable quantities in gneisses, amphibolites, quartzites, and schists of the Keivy and Tundra series [1]. The aluminous metapelites of the Keivy series (predominantly kyanite schists) are rich in carbon (0.1–2.3 wt % on average) [1–3]. These rocks are exposed over a wide area (Figure1) of about 200 km in length and from several hundred meters to 10–14 km in width in the central part of the Keivy Terrane, as well as several smaller bands and lenses in its eastern and southern parts [3]. The rocks are considered to have originated from sediments that accumulated in a shallow water basin in a stable tectonic setting [1,2]. Keivy series schists are metamorphosed unequally. According to References [4–6], most of the stratum was metamorphosed under amphibolite facies conditions at Minerals 2019, 9, 94; doi:10.3390/min9020094 www.mdpi.com/journal/minerals Minerals 2019, 9, 94 2 of 17 Minerals 2019, 9, x FOR PEER REVIEW 2 of 17 T = 450–560 ◦C and P = 4–5.3 kbar. In the central part of the Keivy Terrane (mostly in kyanite schists), metamorphism increased either to T = 550–600 °C and P = 6–6.5 kbar [5], or to T = 540–620 °C and P = metamorphism increased either to T = 550–600 ◦C and P = 6–6.5 kbar [5], or to T = 540–620 ◦C and 5.2–6 kbar [7]. In the east, temperatures were reduced to T < 500 °C (epidote–amphibolite facies, the P = 5.2–6 kbar [7]. In the east, temperatures were reduced to T < 500 ◦C (epidote–amphibolite facies, pressure is not specified) [4,6]. Within the zone of influence of the alkaline granites (the western part the pressure is not specified) [4,6]. Within the zone of influence of the alkaline granites (the western of the Terrane), metamorphism proceeded under the conditions of kyanite–sillimanite subfacies of part of the Terrane), metamorphism proceeded under the conditions of kyanite–sillimanite subfacies of amphibolite facies at T = 550–650 °C and P < 4 kbar [4]. Thermodynamic constructions suggest amphibolite facies at T = 550–650 ◦C and P < 4 kbar [4]. Thermodynamic constructions suggest several several stages of metamorphism [5], but their numbers, ages, and correspondence to geodynamic stages of metamorphism [5], but their numbers, ages, and correspondence to geodynamic events vary events vary between authors [6]. The age of the metapelites is also debatable. Some authors believe between authors [6]. The age of the metapelites is also debatable. Some authors believe that they are that they are Archean [3,6,8–10], while others state that they are Paleoproterozoic [11,12]. However, Archeanreliable dating [3,6,8– 10of ],these while rocks others has state not thatbeen they performed are Paleoproterozoic. In this article, [11 we,12 ].discuss However, previous reliable and dating new of these rocks has not been performed. In this article, we discuss previous and new data on CM, which data on CM, which abounds in the Keivy metapelites as scattered fine particles and larger aboundsintergranular in the flakes. Keivy metapelites as scattered fine particles and larger intergranular flakes. Figure 1.1. GeologicalGeological scheme scheme of of the the Keivy Keivy Terrane Terrane compiled compiled on theon the basis basis of the of 1:500,000the 1:500 Geological,000 Geological Map ofMap the of Kola the RegionKola Region (simplified (simplified after Reference after Reference [13]), showing [13]), showing sampling sampling locations locations (letters in(letter blues circles):in blue (circles)a)—Makzabak: (a)—Makzabak (sillimanite (sillimanite schists); schists); (b)—Rova (b) (quartzolites);—Rova (quartzolites); (c)—Tyapshmanyuk (c)—Tyapshmanyuk (kyanite (kyanite schists); (schists);d)—Shuururta (d)—Shuururta (kyanite schists); (kyanite (e )—Igiurtaschists); (kyanite(e)—Igiurt schists).a (kyanite Legend: schists). 1—mafic Legend: and ultramafic 1—mafic rocks, and PR1;ultramafic 2—Keivy rocks, alkaline PR1; 2 granite—Keivy complex, alkaline AR2;granite 3—gabbroids, complex, AR2; AR2; 3— 4—granitoidsgabbroids, AR2; of normal 4—granitoids alkalinity of (undivided),normal alkalini AR2;ty (undivided), 5—Keivy series AR2; aluminous 5—Keivy schists,series aluminous AR2; 6—Tundra schists, seriesAR2; 6 rocks—Tundra (acidic, series medium, rocks basic(acidic, metavolcanics, medium, basic mica metavolcanics, parashists), AR2;mica parashists), 7—gneisses AR2; and amphibolites7—gneisses and of Kola amphibolites series (basement of Kola complex),series (basement AR; 8—faults. complex), The AR; green 8— linefaults. delineates The green the line boundaries delineates of the Keivyboundaries Terrane. of the The Keivy inset showsTerrane the. The position inset shows of the Keivythe position Terrane of withinthe Keivy the KolaTerrane Peninsula. within the Kola Peninsula. WeWe presentpresent thethe firstfirst datadata onon CMCM fromfrom alkalinealkaline granitesgranites ofof thethe Keivy Terrane.Terrane. TheThe KeivyKeivy alkaline granite complexcomplex hashas an an age age of of 2.67–2.65 2.67–2.65 Ga Ga [14 [14–16–]16] and and it occupiesit occupies an areaan area of more of more than th 2500an 2500 km2 [km17].2 Due[17]. toDue the to poor the poor exposure exposure of the of contact the con zones,tact zones, the relationship the relationship to the to surrounding the surrounding rocks rocks is not is clear. not Thisclear. gives This rise gives to contradictory rise to contradictory interpretations. interpretations. Some authors Some suggested authors asuggest metasomaticed a metasomatic or rheomorphic or genesisrheomorphic of granites genesis ([11 of] andgranites references ([11] and therein). references Others therein) describe. O thethers intrusion describ ofe the granitic intrusion magma of eithergranitic into magma formations either ofinto the formations same tectonomagmatic of the same tectonomagmatic system [18] or into system previously [18] or metamorphosed into previously rocksmetamorphosed [3,17]. These rocks rocks [3,17] are the. T world’shese rocks oldest are rare-metal the world's anorogenic oldest granitesrare-metal [15 ,16anorogenic,19]. In the granites contact zones[15,16,19] between. In the the contact alkaline zon graniteses between and the metamorphicalkaline granit rocks,es and as the well metamorphic as in the internal rocks,part as well of the as graniticin the internal intrusions, part pegmatites of the granitic and quartzolitesintrusions, pegmatites are common. and Following quartzolites [20,21 are], the common. term “quartzolite” Following [20,21], the term “quartzolite” is used for a pegmatitic or hydrothermal rock that is primarily composed of quartz (> 60 vol %). The available geochronological estimates imply the possibility of the diachronous formation of pegmatites and quartzolites: The first formation stage was syngenetic Minerals 2019, 9, 94 3 of 17 is used for a pegmatitic or hydrothermal rock that is primarily composed of quartz (> 60 vol %). The available geochronological estimates imply the possibility of the diachronous formation of pegmatites and quartzolites: The first formation
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