Fenner trend and the role of fractional crystallisation and ferrobasaltic magma immiscibility in granophyre petrogenesis: the case of the mesoproterozoic Valaam sill in the Ladoga graben, Karelia

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Abstract

Petrographic, mineralogical, geochemical, isotope-geochemical studies of granophyres and host ferrogabbro, quartz ferromontsogabbro, quartz montsodiorites, and quartz monzonites in the Mesoproterozoic Valaam sill in the Ladoga Graben on the Karelian craton have been carried out. The sill is poorly layered: ferrogabbros are common in the lower part of the sill, the middle part consists of quartz gabbro-monzonites and quartz monzonites, granophyres form a network of veins mainly in the upper part of the sill. Geochemical features of ferrogabbro, iron-rich composition of olivine and pyroxene, low Ca composition of plagioclase indicate evolution along the Fenner trend. Granophyres have petro- and geochemical characteristics of anorogenic alkaline granites, are characterised by negative Eu/Eu* = = 0.15–0.49 and REE distribution similar to those of granophyres of layered intrusives. All rocks of the sill are characterised by a similar isotopic composition of Sr (87Sr/86Sr)T = 0.7043–0.7066, and εNd values ranging from –9.6 to –11.2. Model calculations show that fractional crystallisation can lead the initial ferrogabbro melt into immiscibility. Ilmenite-magnetite-silicate microstructures have been identified in ferrogabbro and ferromontzogabbro from the sill; similar microstructures in layered intrusives are considered evidence for immiscibility of Fe-enriched and Si-enriched liquids (Holness et al., 2011; Dong et al., 2013). The segregation of the high-silica melt may have occurred in a crustal chamber at around 350 MPa and 960oC; the sill formation at around 70 MPa injected magma in the form of a crystalline mush through which acidic melt migrated. This melt underwent fractional crystallisation and reacted with host minerals. At the level of sill formation, it crystallised under supercooling into granophyre aggregates. The example of the Valaam sill shows that after fractionation according to the classical Fenner trend reaches the final composition – ferrogabbro, its continuation with a conjugate decrease in SiO2 and Fe contents can be associated with incomplete separation and mixing of iron-rich melts and separated acidic melt. Such a mechanism can be realised during the formation of the mafic part of AMCG-type massifs.

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About the authors

А. А. Nosova

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Author for correspondence.
Email: nosova@igem.ru
Russian Federation, Moscow

N. М. Lebedeva

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Email: nosova@igem.ru
Russian Federation, Moscow

A. A. Vozniak

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Email: nosova@igem.ru
Russian Federation, Moscow

L. V. Sazonova

Lomonosov Moscow State University

Email: nosova@igem.ru

Geological Department

Russian Federation, Moscow

I. A. Kondrashov

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Email: nosova@igem.ru
Russian Federation, Moscow

Y. O. Larionova

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Email: nosova@igem.ru
Russian Federation, Moscow

Е. V. Коvalchuk

Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences

Email: nosova@igem.ru
Russian Federation, Moscow

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2. Fig. 1. (a) Geological position of the Valaam sill in the structures of the northwest of the East European Craton according to (Brander, Söderlund, 2007) and (Grabarczyk et al., 2023), with additions. The rectangle highlights the area shown in (b). (b) Geological scheme of the Northern Ladoga region shows the position of the Valaam sill within the Ladoga graben in the junction area of ​​the Karelian Craton and the Svecofennian orogenic region. 1, 2: volcanic association of the Ladoga graben: 1 – Valaam sill, ferrogabbro, quartz ferromonzogabbro, monzodiorites, quartz monzonites, graphic leucogranites (µМР1v); 2 – ferrobasalts, Salmi Formation (βMP1sl); 3 – siltstones, sandstones, Priozersk and Salmi suites (МР1pr+sl); 4 – Salmi massif of AMCG type (ργМР1). 5–11: Svecofennian orogenic region: 5 – Elisenvaara-Vuoksi monzogabbro-monzonite-syenite-granite complex (µν-γµPR3ev); 6 – diorite-mafic complex (νβPR1); 7 – Kurkiek norite-enderbite (νePR1k) and 8 – diorite-tonalite Impiniem and Yakkim ((δ-ργPR1im δPR1j) complexes; 9 – undifferentiated granites (γPR3); 10 – Ladoga series, biotite gneisses, quartz-mica schists and other metamorphites (PR1ld); 11 – Isojarvin metamorphic sequence, metatuffites (PR1). 12 – syn-folded undifferentiated plutonic complexes, migmatites, granites (mαγAR3); 13 – migmatite-plagiogranite complexes of the Karelian Craton (mργAR2–3); 14 – faults: a – reliable, b – inferred; 15 – Meyer thrust. (c) – region works. Geological basis according to (Maksimov et al., 2015; Stepanov et al., 2004), with changes; geological schemes of the areas of detailed works on the islands, shown by rectangles in (b): 16 – ferrogabbo; 17 – quartz monzonites, 18 – amphibole quartz monzonites; 19 – veins: a – quartz monzonites, b – graphic leucogranites; 20 – contours of rock varieties; 21 – observation points: a – used in this work and in Supplementary 1, ESM_1, b – others.

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3. Fig. 2. Veins of graphic leucogranite and quartz monzonite in the Valaam sill: (a) and (b) veins in quartz ferromonzogabbro on Lunkulunsaari Island; (c) vein of quartz monzonite in ferrogabbro in the northwestern part of Valaam Island; (d) gently sloping vein of leucogranites in quartz ferromonzogabbro in the southeastern part of Valaam Island; (d) pipe of graphic leucogranite in quartz ferromonzogabbro, Lunkulunsaari Island; (e) scans of thin sections in accordance with the sampling location in Fig. 2e.

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4. Fig. 3. Backscattered electron (BSE) photographs of the Valaam sill rocks. (a) ferrogabbro, orthopyroxene grows on ferrous olivine grains, symplectite-like intergrowths of ilmenite and magnetite are clearly visible, as well as individual grains of magnetite and apatite (sample 21S-21); (b) quartz ferromonzogabbro. Overgrowth of K-feldspar is observed on plagioclase grains, the spaces between large feldspar grains are filled with granophyre intergrowths of potassium feldspar and quartz (sample 22Ld-06); (c) contact zone between quartz ferrogabbro (right) and the granophyre part of the vein monzonite sample (left). At the contact, there is an increase in K-feldspar on plagioclase grains and replacement of clinopyroxene by chlorite and biotite (sample 21C-22); (d) contact between a vein of graphic leucogranite and quartz ferrogabbro. Rounded clinopyroxene grains are replaced by biotite and actinolite, symplectite-like intergrowths of ilmenite with amphibole are present, apatite is confined to ilmenite and replaced clinopyroxene grains. The gaps are filled with a granophyre aggregate (sample 22Ld-16); (d) graphic leucogranite, feldspar grains are completely or partially replaced by small granophyre intergrowths (GR), onto which larger granophyre intergrowths grow, there are preserved relics of feldspar of a spotted appearance (sample 22Ld-06); (e) graphic leucogranite, granophyre intergrowths of alkali feldspar and quartz develop between feldspar laths, late anhedral masses of quartz and biotite develop in the spaces between the granophyre intergrowths (sample 22Ld-13); (g) graphic leucogranite, a vein filled with quartz and K-feldspar, smoothly turning into granophyre intergrowths of potassium feldspar and quartz (sample 22Ld-06); (z) contact zone between graphic leucogranite and quartz ferrogabbro. At the contact between ferrogabbro, composed of intergrowths of plagioclase and pyroxene, there is an increase in KFS on plagioclase and replacement of clinopyroxene grains by amphibole, a thin vein filled with quartz and carbonate passes through the granophyre, and cavities filled with carbonate are also found in the granophyre (sample 22Ld-06).

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5. Fig. 4. Microstructures of zircon (a–b, sample 22Ld-32a) and quartz (c–e, sample 22Ld-25) precipitates in graphic leucogranites. (a) and (b) – CL images, zircon luminesces in yellow tones with dark gray veins, apatite is greenish-yellow. (c), (d) and (e) – CL images, quartz luminesces in blue tones, lighter areas have higher Ti concentrations, isolated grains show well-defined growth zoning with dark cores and light peripheral zones; alkali feldspar glows in red tones. (c) – BSE image of the same area as in (d) in CL rays. In the upper left corner in (d) – light gray, in (e) – black – rutile precipitates intergrown with quartz. The circles and numbers next to them are the microprobe analysis points and their numbers.

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6. Fig. 5. (a) Compositional diagram of pyroxenes from the Valaam sill rocks in the Fe2Si2O6–Mg2Si2O6–CaFeSi2O6–CaMgSi2O6 coordinates. In addition, compositional fields of pyroxenes from granophyres of the Skaergaard massif (Holness et al., 2011), monzosyenites of the Lofoten massif (Coint et al., 2020) and from experimental basaltic melts crystallized at oxygen fugacity corresponding to QFM and +2ΔQFM (Zhang et al., 2023) are presented. (b) Compositional diagram of feldspars from the Valaam sill rocks in the An–Ab–Or coordinates. Additionally, the composition fields of feldspars from granophyres of the Skeergaard massif (Holness et al., 2011) and monzosyenites of the Lofoten massif (Coint et al., 2020) were extracted.

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7. Fig. 6. Harker diagrams for the rocks of the Valaam sill in comparison with the published compositions of the rocks of the Valaam sill (Sviridenko, Svetov 2008), the rocks of the Salmi massif (Sharkov, 2010), the acidic rocks of the Masurian complex of the AMCG type with an age of 1.49 Ga (Grabarchuk, 2023) and experimental data for the crystallization of basalts of the Emeishian province (Zhang et al., 2023).

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8. Fig. 7. (a) SiO2–(Na2O + K2O) diagram for the rocks of the Valaam sill and (b) crystallization trend in the AFM diagram of the rocks of the Valaam sill and the Salmi massif. For the Valaam sill, data are also given from (Sviridenko, Svetov, 2008), for the Salmi massif from (Sharkov, 2010; Larin, 2011), for the Masurian complex from (Grabarchuk et al., 2023).

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9. Fig. 8. Characteristics of graphic leucogranites by: (a) SiO2 and (Na2O + K2O – CaO) content, boundaries between alkaline, alkaline-calcite, calc-alkaline and calcite granitoids according to (Frost, Frost 2011); (b) the content of alumina A/NK (Al2O3/(Na2O + K2O)–A/CNK (Al2O3/(CaO + Na2O + K2O), in moles; (c) the Fe index (FeO + 0.9Fe2O3)/(FeO + 0.9Fe2O3 + MgO) (Frost et al., 2001) in comparison with the acidic rocks of the Valaam sill (Sviridenko, Svetov, 2008), Salmi massif (Sharkov, 2010) and Pietkowo massif in Poland (Grabarchuk et al., 2023)

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10. Fig. 9. Rocks of the Valaam sill, normalized to (a) CI chondrite (Sun, McDonough, 1989); the mafic and intermediate rocks have similar distribution spectra with a weak positive anomaly Eu/Eu* = 1.1–1.2, in the graphic leucogranites a negative anomaly Eu/Eu* = 0.15–0.49 is observed. Normalized to (b) primitive mantle after (Sun, McDonough, 1989). Negative anomalies of Sr, Nb, Ta and Ti are observed in all rocks, a positive P-anomaly is characteristic of ferrogabbro; positive anomalies of K, Zr and Hf appear in the graphic leucogranites.

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11. Fig. 10. Results of modeling the evolution of the Valaam sill melts in Melts on Harker diagrams. Model 1 for a dry melt (0.2 wt.% H2O) under reducing conditions (ΔQFM-1) and model 2 for a melt with a higher water content (1.2 wt.% H2O) under more oxidizing conditions (QFM) are shown. Asterisks indicate the compositions of the Valaam sill melts. Also shown are the compositions of high-Ti and low-Ti basalts of the Emeishian province as an example of typical continental tholeiites and the evolution of tholeiitic basalt melts in the experiments (Zhang et al., 2023) and (Botcharnikov et al., 2008) for hydrous (–h) and dry (–d) conditions.

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12. Fig. 11. The εNd–age (million years) diagram for the rocks of the Ladoga region. For the rocks of the Valaam Sill, our data and data from (Ramo 1991) were used, for the rocks of the Salmi Massif – from (Larin, 2011). The purple area shows the evolutionary trend for the Paleoproterozoic rocks of the North Ladoga region (Konopelko et al., 2005), for the Archean rocks of the western Karelian Craton – from (Larionova et al., 2007).

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13. Fig. 12. Comparison of natural and model compositions of the Valaam sill melts with natural and experimental compositions in which immiscibility between Si- and Fe-enriched melts was observed. (a) Models 1 and 2 of the evolution of the Valaam sill melts calculated in Melts, and the lines of experimental compositions of high-Ti - green dotted line and low-Ti - red dotted line of tholeiitic basalts (Zhang et al., 2023); gray line - Melts model for high-Ti basalt from experiments (Zhang et al., 2023). The position of the bimodal is shown by the solid line after (Zhang et al., 2023) and the dotted line - after (Charlier, Grove, 2012). NBO/T is the proportion of non-bridging oxygens in the melt. (b) – compositions of the rocks of the Valaam sill (asterisks) and models 1 and 2 of the evolution of Valaam melts calculated in Riolythe-Melts, compositions of Si- (blue field) and Fe- (brown field) enriched melts obtained in the experiments (Lino et al., 2023), as well as compositions of the rocks of the Limeira massif, which were used as starting compositions in these experiments (gray field) and aplites in this massif (Lino et al., 2023); the position of the boundary of the immiscibility region (blue line) is shown for alkali-enriched tholeiitic basalt according to (Lino et al., 2023).

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14. Fig. 13. Microstructures of Fe-Ti oxide segregations in quartz monzonites of the Valaam sill: (a) – Fe-Ti oxide segregation embedded in granophyre aggregate, segregation consists of thin intergrowths of ilmenite and alkali feldspar in the center, contains inclusions of apatite, ilmenite is partially replaced by titanite, the marginal part of the segregation is composed of magnetite; (b) – detail in Fig. (a), highlighted by red rectangle, BSE; (c) – ilmenite-silicate intergrowth in the central part of the segregation and with a peripheral part of ilmenite with rounded sulfide inclusions, another rounded sulfide segregation nearby, in the upper right part of the image, reflected light; (g) – Fe-Ti oxides precipitate in the form of fine intergrowths of ilmenite with alkali feldspar, surrounded by magnetite with euhedral contours, BSE; (d) – coarse worm-like intergrowths of ilmenite with amphibole, with a rim of magnetite, BSE; (e) – ilmenite-silicate intergrowths (marked with a red arrow) in a granophyre aggregate, BSE; (g) – ilmenite-titanite-apatite intergrowth in a granophyre aggregate, BSE.

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15. Fig. 14. Zr/Hf–Nb/Ta (a) and Ba–Rb/Sr (b) diagrams for the rocks of the Valaam sill and the Salmi pluton. The acidic rocks of the Valaam sill fall into the region of weakly fractionated rocks; for comparison, the data for strongly fractionated granites from (Wu et al., 2017) and the data for the Salmi pluton from (Larin, 2011) are plotted.

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16. Fig. 15. Schematic representations of the crystallization order of the initial melt of the Valaam sill rocks: (a) magmatic stage, early crystallization of clinopyroxene and plagioclase crystals, evolution of the main melt into monzonite; (b) magmatic stage, continuation of fractional crystallization; separation into high-Fe melt in the form of droplets in the matrix of high-Si melt; (c) magmatic stage, continuation of fractional crystallization, formation of clusters of high-Fe melt in the form of ilmenite intergrowths, crystallization of amphibole rims on clinopyroxene and potassium feldspar rims on plagioclase from the acid melt; (d) late magmatic stage, formation of granophyre structure, formation of micromiaroles, interaction with the host rocks.

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17. Supplementary 1, ESM – Location of the studied samples on the islands of Valaam, Lunkulunsaari
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18. Supplementary 2, ESM – Methods
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19. Supplementary 3, ESM – Mineral Compositions
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20. Supplementary 4, ESM – Chemical composition of the studied samples of the Valaam sill
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21. Supplementary 5, ESM – Ti concentration in quartz and calculation of saturation temperature for Zr
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22. Supplementary 6, ESM – Model 1 of fractional crystallization of ferrogabbro melt calculated in the Melts software package
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23. Supplementary 7, ESM – Model 2 of fractional crystallization of ferrogabbro melt calculated in the Melts software package
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24. Supplementary 8, ESM – Mass balance calculation of fractional crystallization of ferrogabbro melt
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