Ultramafic-alkaline-carbonatite Tajno intrusion in NE Poland: A new hypothesis about the massif formation and related mineralization
Anna GrabarczykGrzegorz GilYan LiuJakub KotowskiPetras JokubauskasJaime D. BarnesKrzysztof NejbertJanina WiszniewskaBogusław Bagiński
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This manuscript presents results of the newest petrographic, mineralogical and bulk chemical, as well as H, C and O stable isotope study of carbonatites and associated silicate rocks from the Tajno Massif (NE Poland). The Tajno Intrusion is a Tournaisian-Visean ultramafic-alkaline-carbonatite body emplaced within the Paleoproterozoic rocks of the East European Craton (EEC). Carbonatites of the Tajno Massif can be subdivided into the calciocarbonatite (calcite), ferrocarbonatite (ankerite), and breccias with an ankerite-fluorite matrix. Due to location at the cratonic margin and abundance in the REE, Tajno classifies (Hou et al., 2015) as the carbonatite-associated REE deposit (CARD), and more precisely as the Dalucao-Style orebody (the breccia-hosted orebody). High Fe2O3 (13.8 wt%), MnO (2.1 wt%), total REE (6582 ppm), Sr (43895 ppm), Ba (6426 ppm), F (greater than10000 ppm) and CO2 contents points for the involvement of the slab – including pelagic metalliferous sediments – in the carbonatites formation. Spatial relations and Sr isotope composition ((87Sr/86Sr)i = 0.7043–0.7048; Wiszniewska et al., 2020) of alkali clinopyroxenite and syenite suggest that these are products of differentiation of the magma, generated by the initial melting of the SCLM due to influx of F-rich fluids from subducted marine sediments. Carbonatites Sr isotope composition ((87Sr/86Sr)i = 0.7037–0.7038), and Ba/Th (16–20620) and Nb/Y (0.01–6.25) ratios, link their origin with a more advanced melting of the SCLM, triggered by CO2-rich fluids from the subducted AOC and melts from sediments. The Tajno Massif – and coeval mafic-alkaline intrusions – age, high potassic composition, and location along the craton margin nearly parallel the Variscan deformation front, are suggesting Variscan subduction beneath the EEC. The oxygen isotope compositions of clinopyroxene (δ18O value = 5.2‰) and alkali feldspar (δ18O value = 5.7‰), from alkali clinopyroxenite and foid syenite, respectively, are consistent with mantle-derived magmas. Isotopic compositions of carbonatites and breccias (carbonate δ18O = 8.7‰ to 10.7‰; δ13C = -4.8‰ to −0.4‰) span from values of primary carbonatites to carbonatites affected by a fractionation or sedimentary contamination. The highest values (δ18O = 10.7‰; δ13C = -0.4‰) were reported for breccia cut by numerous veins confirming post-magmatic hydrothermal alteration. The lowest carbonate δ18O (9.3‰ to 10.7‰) and δ13C (−5.0‰ to −3.8‰) values are reported for veins in alkali clinopyroxenites, whereas the highest δ18O (11.2‰) and δ13C (−1.2‰ to −1.1‰) values are for veins in syenites and trachytes. Isotopic composition of veins suggests hydrothermal origin, and interaction with host mantle-derived rocks, as well as country rocks. In silicate rocks of the Tajno Massif, fluid influx leads to the development of Pb, Zn, Cu, Ag, Au sulfide mineralization-bearing stockwork vein system, with carbonate, silicate and fluorite infilling the veins. Bulk-rock contents of molybdenum (925 ppm), rhenium (905 ppb) and palladium (29 ppb) are notable. The Re-rich molybdenite association with galena, pyrite and Th-rich bastnäsite in carbonate veins is similar as in Mo deposits associated with carbonatites, implying the mantle source of Mo and Re.Keywords:
Carbonatite
Ultramafic rock
Massif
Breccia
Baddeleyite
Lile
Ankerite
Protolith
Carbonatites are rare igneous carbonate-rich rocks. Most carbonatites contain a large number of accessory oxide, sulfide, and silicate minerals. Baddeleyite (ZrO2) and zircon (ZrSiO4) are common accessory minerals in carbonatites and because these minerals host high concentrations of U and Th, they are often used to determine the ages of formation of the carbonatite. In an experimental study, we constrain the stability fields of baddeleyite and zircon in Ca-rich carbonate melts with different silica concentrations. Our results show that SiO2-free and low silica carbonate melts crystallize baddeleyite, whereas zircon only crystallizes in melts with higher concentration of SiO2. We also find that the zirconsilicate baghdadite (Ca3ZrSi2O9) crystallizes in intermediate compositions. Our experiments indicate that zircon may not be a primary mineral in a low-silica carbonatite melt and care must be taken when interpreting zircon ages from low-silica carbonatite rocks.
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Silicate minerals
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Despite extensive industrial application, global scandium resources are uncertain. Although Sc is mainly supplied as a by-product of mining of rare earth metals, uranium or aluminum, it is also concentrated by carbonatite process, both magmatic and post-magmatic. In this paper, we report data on Sc distribution within the Kovdor baddeleyite–apatite–magnetite deposit (phoscorite–carbonatite pipe) in the Murmansk Region of Russia, which seems to be a significant reservoir of this "strategic" metal. We show that baddeleyite is the main Sc-concentrating mineral, and reveal the spatial distribution of Sc-bearing baddeleyite within the Kovdor phoscorite–carbonatite pipe. The scandium content in baddeleyite differs according to the petrographic zonation of the pipe culminating in the inner (axial) zone of the pipe and in dolomite carbonatites cutting the pipe. We have estimated the amount of Sc2O3 in the Kovdor deposit as amounting to 420 t at average content in baddeleyite of 0.078 wt.%, and revealed the economic potential for Sc recovery as a by-product. Other Sc-bearing minerals – pyrochlore and ilmenite groups, zirconolite, and juonniite – have been described and opportunity of Sc recovery was examined, too.
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The pyrochlore supergroup minerals (PSM) are typical secondary phases that replace (with zirconolite–laachite) earlier Sc-Nb-rich baddeleyite under the influence of F-bearing hydrothermal solutions, and form individual well-shaped crystals in surrounding carbonatites. Like primary Sc-Nb-rich baddeleyite, the PSM are concentrated in the axial carbonate-rich zone of the phoscorite-carbonatite complex, so their content, grain size and chemical diversity increase from the pipe margins to axis. There are 12 members of the PSM in the phoscorite-carbonatite complex. Fluorine- and oxygen-dominant phases are spread in host silicate rocks and marginal carbonate-poor phoscorite, while hydroxide-dominant PSM occur mainly in the axial carbonate-rich zone of the ore-pipe. Ti-rich PSM (up to oxycalciobetafite) occur in host silicate rocks and calcite carbonatite veins, and Ta-rich phases (up to microlites) are spread in intermediate and axial magnetite-rich phoscorite. In marginal (apatite)-forsterite phoscorite, there are only Ca-dominant PSM, and the rest of the rocks include Ca-, Na- and vacancy-dominant phases. The crystal structures of oxycalciopyrochlore and hydroxynatropyrochlore were refined in the Fd3¯m space group with R1 values of 0.032 and 0.054 respectively. The total difference in scattering parameters of B sites are in agreement with substitution scheme BTi4+ + YOH‒ = BNb5+ + YO2‒. The perspective process flow diagram for rare-metal “anomalous ore” processing includes sulfur-acidic cleaning of baddeleyite concentrate from PSM and zirconolite–laachite impurities followed by deep metal recovery from baddeleyite concentrate and Nb-Ta-Zr-U-Th-rich sulfatic product from its cleaning.
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Wang et al. (2023) propose that rocks adjacent to the Panzhihua intrusion are not marbles and skarns, but carbonatites. If true, this interpretation could have important implications for models explaining the origin of the large Fe-Ti ore deposits in the intrusion. We reject this interpretation for two principal reasons: 1) the objects described as "mantle xenoliths", and considered, incorrectly, as diagnostic of carbonatite, are in fact deformed and altered mafic/ultramafic intrusions; 2) the concentrations of incompatible trace elements in the marbles are low and typical of metasedimentary rocks, not carbonatite.
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