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This contribution presents U-Pb geochronological data for Ca-Fe-Ti garnets from compositionally diverse alkaline and carbonatitic intrusive rocks ranging from Neoarchean to Permian-Triassic (Cinder Lake and Eden Lake in Manitoba, Canada; Belaya Zima and Odikhincha in Siberia, Russia; Afrikanda in the Kola Peninsula, Russia) obtained using isotope-dilution thermal-ionization mass spectrometry (ID-TIMS) and their trace-element compositions measured by laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICPMS). The studied garnets yield U-Pb concordant or subconcordant ages obtained with a precision of <0.5% owing to their relatively high content of U and negligible common Pb. The new ID-TIMS data are in excellent agreement with the previously reported zircon, baddeleyite and perovskite ages. The results of the present work demonstrate that postmagmatic alteration does not disturb or reset the U-Pb isotopic budget of these minerals, and that garnets representing the andradite-schorlomite-morimotoite system can serve as a robust reference material for micro-analytical geochronological studies of a wide spectrum of igneous and contact-metasomatic rocks. The new LA-ICPMS data demonstrate that the abundances of rare-earth, high-field-strength and other trace elements in calcic garnets from alkaline and carbonatitic rocks vary by at least two orders of magnitude and can therefore be used as reliable magma-evolution tracers. The rare-earth budget of these minerals is best described in terms of the chondrite-normalized ratios (Sm/La) cn and (Sm/Yb) cn , which are sensitive to lanthanide fractionation, and Y/Ho, which is interpreted to respond to garnet re-equilibration with a fluid. • U-Pb ID-TIMS study of calcic garnets yields precise and reliable ages. • Postmagmatic alteration does not disturb the U-Pb isotopic budget. • Ca-Fe-Ti garnets can serve as a robust isotopic reference material. [ABSTRACT FROM AUTHOR]

Vladykinite, ideally Na3Sr4(Fe2+Fe3+)Si8O24, is a new complex sheet silicate occurring as abundant prismatic crystals in a dike of coarse-grained peralkaline feldspathoid syenite in the north-central part of the Murun complex in eastern Siberia, Russia (Lat. 58° 22' 48" N; Long. 119° 03' 44" E). The new mineral is an early magmatic phase associated with aegirine, potassium feldspar, eudialyte, lamprophyllite, and nepheline; strontianite (as pseudomorphs after vladykinite) and K-rich vishnevite are found in the same assemblage, but represent products of late hydrothermal reworking. Vladykinite is brittle, has a Mohs hardness of 5, and distinct cleavage on {100}. In thin section, it is colorless, biaxial negative [α = 1.624(2), β = 1.652(2), γ = 1.657(2), 2Vmeas = 44(1)°, 2Vcalc = 45(1)°] and shows an optic orientation consistent with its structural characteristics (X^a = 5.1° in β obtuse, Z^c = 4.7° in β acute, Y = b). The Raman spectrum of vladykinite consists of the following vibration modes (listed in order of decreasing intensity): 401, 203, 465, 991, 968, 915, 348, 167, 129, 264, 1039, and 681 cm-1; O-H signals were not detected. The Mössbauer spectrum indicates that both Fe2+ and Fe3+ are present in the mineral (Fe3+/Fe∑ = 0.47), and that both cations occur in a tetrahedral coordination. The mean chemical composition of vladykinite (acquired by wavelength-dispersive X-ray spectrometry and laser-ablation inductively-coupled-plasma mass-spectrometry), with FeΣ recast into Fe2+ and Fe3+ in accord with the Mössbauer data, gives the following empirical formula calculated to 24 O atoms: (Na2.45Ca0.56)Σ3.01(Sr3.81K0.04Ba0.02La0.02Ce0.01)Σ3.90(Fe0.752+Fe0.663+Mn0.26Zn0.16Al0.12Mg0.05Ti0.01)γ2.01(Si7.81Al0.19)Σ8.00O24. The mineral is monoclinic, space group P21/c, a = 5.21381(13), b = 7.9143(2), c = 26.0888(7) Å, β = 90.3556(7)°, V = 1076.50(5) ų, Z = 2. The ten strongest lines in the powder X-ray diffraction pattern are [dobs in Å (I) (hkl)]: 2.957 (100) (123, 123); 2.826 (100) (117, 117); 3.612 (58) (114, 114); 3.146 (37) (120); 2.470 (32) (210, 01.10); 4.290 (30) (111, 111); 3.339 (30) (106, 115, 106); 2.604 (28) (200); 2.437 (25) (034); 1.785 (25) (21.10, 234). The structure of vladykinite, refined by single-crystal techniques on the basis of 3032 reflections with F0 > 4σF0 to R1 = 1.6%, consists of tetrahedral sheets parallel to (100) and consisting of (Si8O24)16- units incorporating four-membered silicate rings and joined into five- and eight-membered rings by sharing vertices with larger tetrahedra hosting Fe2+, Fe3+, Mn, Zn, Al, Mg, and Ti. Larger cations (predominantly Na, Sr, and Ca) are accommodated in octahedral and square-antiprismatic interlayer sites sandwiched between the tetrahedral sheets. Structural relations between vladykinite and other sheet silicates incorporating four-, five-, and eight-membered rings are discussed. The name vladykinite is in honor of Nikolay V. Vladykin (Vinogradov Institute of Geochemistry, Russia), in recognition of his contribution to the study of alkaline rocks. Holotype and co-type specimens of the mineral were deposited in the Robert B. Ferguson Museum of Mineralogy in Winnipeg, Canada. [ABSTRACT FROM AUTHOR]

This work is the first in situ U–Pb geochronological study of perovskite and calcic garnet (andradite) from the Guli complex in the Maimecha–Kotuy alkaline province (Polar Siberia, Russia). The U–Pb isotopic compositions of perovskite from contact zones of the two carbonatite stocks (Southern and Northern) and from jacupirangite separating the stocks were determined by laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICPMS) and isotope-dilution thermal-ionisation mass-spectrometry (ID-TIMS). The LA-ICPMS and ID-TIMS data for perovskite from the Northern carbonatite stock are in good agreement, yielding 206Pb/238U ages of 250.4 ± 1.1 Ma and 249 ± 2 Ma, respectively. These ages are also within the analytical uncertainty from the ID-TIMS results for perovskite from jacupirangites (250 ± 1 Ma). The LA-ICPMS results for perovskite from the Southern carbonatite stock indicate its somewhat older age (255.3 ± 2.4 Ma), implying the possibility of small-volume mantle magmatism predating the eruption of the Siberian flood basalts at ca. 252–251 Ma. This interpretation is supported by reports of pre-flood magmatism elsewhere in eastern Siberia. Andradite crystals from the contact between the Southern stock and metasomatised melilitolite were analysed by ID-TIMS. These measurements are inconclusive (247 ± 6 Ma) and could not be used to constrain further the timing of carbonatitic magmatism in the southern part of the complex. The present contribution also presents a refined methodology for LA-ICPMS geochronological studies of perovskite with elevated levels of common lead, and addresses some of the problems with previously proposed calibration standards. [ABSTRACT FROM AUTHOR]