A1-type granite xenoliths occur in alkali basalts erupted during Pliocene–Pleistocene continental rifting of Carpathian back-arc basin (Central Europe). The Pliocene (5.2 Ma) peraluminous ...calc-alkalic granite contains unusually high concentrations of critical metals bound in Nb, Ta, REE, U, Th-oxides typical for silica-undersaturated alkalic granites, and syenites: columbite-Mn, fergusonite-Y, oxycalciopyrochlore, Nb-rutile, and Ca-niobate (fersmite or viggezite). In contrast, it does not contain allanite and monazite—the main REE-carriers in calc-alkalic granites. The crystallization of REE-bearing Nb-oxides instead of OH-silicates and phosphates was probably caused by strong water deficiency and low phosphorus content in the parental magma. Increased Nb and Ta concentrations have been inherited from the mafic parental magma derived from the metasomatized mantle. The strong Al- and Ca-enrichment probably reflects the specific composition of the mantle wedge modified by fluids, alkalic, and carbonatitic melts liberated from the subducted slab of oceanic crust prior to the Pliocene-Pleistocene rifting.
This article proposes an improved approach to monazite dating by electron microprobe that includes a “monazite age reference correction” (MARC). During analysis, a set of differing monazite standard ...reference materials with established isotopic ages are measured at the start of the session. These measurements are used to test the analytical set-up and, if necessary, to calculate MARC factors that can be applied to monazite samples. The MARC is not intended as a way to correct systematic errors due to problems in set-up, but rather as a fine-scale adjustment for factors that cannot be readily assessed during single sessions. Long-term, multi-session calculation of MARC factors allows for precise monitoring of anomalous behavior among monazite age reference materials during individual sessions. The method can also assist in the identification of chemical inhomogeneity in monazite, such as that commonly produced by interaction with metasomatic fluids. A representative set of electron microprobe monazite age reference materials are presented, including two ‘reference monazites’ that are good examples of monazite with age disturbance induced by metasomatism. Additional modifications to analytic protocols are proposed, including a) corrections for count rate increases during long beam dwell times, and b) improved estimation of background values at line positions by accounting for the effect of mean atomic number.
•improved monazite dating by EPMA that includes a ‘monazite age reference correction’ (MARC)•consistent analytical method for monazite age determination•correction of Th, U, Pb and Y count-rate increase over long acquisitions•estimation of exponential background at PbMα via lin-exp - MAN (mean atomic number) dependency•test internal integrity within the set of monazite reference materials and detect problematic
An uncommon assemblage of primary and secondary accessory REE minerals was identified in a Permian A-type granite clast in polymict conglomerates intercalated in the Cretaceous flysch sequence of the ...Pieniny Klippen Belt, Western Carpathians, northwest Slovakia. A detailed electron-microprobe study of the granite reveals extensive subsolidus alteration of primary magmatic allanite-(Ce) to ferriallanite-(Ce) and fluorapatite. The Y, Ce-rich fluorapatite was replaced by the dissolution–reprecipitation process to the britholite group mineral members: fluorbritholite-(Y), britholite-(Y), fluorcalciobritholite, and its hydroxyl-dominant analogue (“calciobritholite”). Britholite-(Y) contains up to 5.2wt.% ThO2 (0.15 apfu Th); the highest Th content yet reported in naturally occurring Y-dominant britholites. Moreover, the alteration of (ferri)allanite-(Ce) resulted to complex pseudomorphs and overgrowths, including mainly REE carbonate phases: synchysite-(Ce) to its hydroxyl-dominant analogue “hydroxylsynchysite-(Ce)”, bastnäsite-(Ce) and calcite, rarely monazite-(Ce), epidote, clinochlore, titanite, TiO2 phase, and pseudorutile. In some cases, secondary carbonate minerals (mainly synchysite and calcite) replaced a substantial part of former allanite crystals. Moreover, primary magmatic biotite (annite) was partly transformed to acicular stilpnomelane. Textural and compositional data indicate extensive replacement and breakdown of the primary magmatic allanite and apatite by aqueous fluids rich in fluorine and carbon, liberated during a younger post-magmatic, low-temperature hydrothermal-metamorphic overprint of the granite.
•Subsolidus low-temperature overprint of primary minerals in A-type granite•Alteration of magmatic Y,REE-rich fluorapatite to britholite group minerals•The highest Th content yet reported in Y-dominant britholites (5.2wt.% ThO2)•Secondary REE carbonates, monazite, and calcite: products of allanite replacement•A role of aqueous hydrothermal-metamorphic fluids rich in fluorine and carbon
During the Łate Cretaceous to Palaeogene, the Magura Basin was supplied by clastic material from source areas situated on the northern and southern margins of the basin, which do not outcrop on the ...surface at present. The northern source area is traditionally connected with the Silesian Ridge, whereas the position of the southern one is still under discussion. A source area situated SE of the Magura Basin supplied the Eocene pebbly para-conglomerates containing partly exotic material. The studied clastic material contains fragments of crystalline rocks, and frequent clasts of Mesozoic to Palaeogene deep and shallow-water limestones. Numerous mica schists, scarce volcanites and granitoids as well as gneisses, quartzites and cataclasites were found in the group of crystalline exotic pebbles. Monazite ages of “exotic” mica-schist pebbles from the Tylicz, Zarzecze and Piwniczna-Mniszek sections document the Variscan 310±10 Ma age of metamorphic processes. The provenance of these exotic rocks could be connected with a remote source area located SE of the Magura Basin, which could be the NW part of the Dacia Mega Unit. The idea is strongly supported by palaeotransport directions from the SE, the absence of material derived from the Pieniny Klippen Belt, the presence of shallow water limestones, typical facies of the Median Dacides belt and metamorphic age distribution proved by monazite dating.
The accessory mineral assemblage (AMA) of igneous cumulate xenoliths in volcanoclastic deposits and lava flows in the Carpathian back-arc basin testifies to the composition of intrusive complexes ...sampled by Upper Miocene-Pliocene basalt volcanoes. The magmatic reservoir beneath Pinciná maar is composed of gabbro, moderately alkalic to alkali-calcic syenite, and calcic orthopyroxene granite (pincinite). The intrusive complex beneath the wider area around Fiľakovo and Hajnáčka maars contains mafic cumulates, alkalic syenite, carbonatite, and calc-alkalic granite. Both reservoirs originated during the basaltic magma underplating, differentiation, and interaction with the surrounding mantle and crust. The AMA of syenites is characterized by yttrialite-Y, britholite-Y, britholite-Ce, chevkinite-Ce, monazite-Ce, and rhabdophane(?). Baddeleyite and REE-zirconolite are typical of alkalic syenite associated with carbonatite. Pyrochlore, columbite-Mn, and Ca-niobates occur in calc-alkalic granites with strong peralkalic affinity. Nb-rutile, niobian ilmenite, and fergusonite-Y are crystallized from mildly alkalic syenite and calc-alkalic granite. Zircons with increased Hf/Zr and Th/U ratios occur in all felsic-to-intermediate rock-types. If rock fragments are absent in the volcanic ejecta, the composition of the sub-volcanic reservoir can be reconstructed from the specific AMA and zircon xenocrysts–xenolith relics disintegrated during the basaltic magma fragmentation and explosion.
Late Ediacaran to Cambrian metagranitoids from the northern Veporic unit of the Western Carpathians show imprints of three metamorphic events, which can be assigned to the Cenerian, Variscan, and ...Alpine orogenies based on electron microprobe dating of monazite. Metamorphic monazites in the metagranitoids are mostly of the Lower to Middle Ordovician age (480–460 Ma). The Ordovician monazite formed in equilibrium with the metamorphic assemblage garnet, biotite, kyanite, ilmenite and quartz at P-T conditions of 6–7 kbar and 550–570 °C, thus providing clear evidence for Cenerian metamorphism in the Western Carpathians. Variscan metamorphism caused minor monazite growth/recrystallization at 364 ± 13 Ma and produced a new mineral assemblage garnet, kyanite, rutile and phengite at P-T conditions of 20–22 kbar and 670–690 °C. The low-grade Alpine metamorphism is recorded by monazite of Cretaceous age (96 ± 23 Ma), but only in orthogneiss of extremely low-Ca composition.
The Veporic metagranitoids show incomplete transformation from magmatic stage, still preserving remnants of plagioclase, K-feldspar and high-Ti biotite. This indicates that the metagranitoids remained relatively dry and failed to complete metamorphic reactions due to kinetic factors at fluid-deficient conditions. Nevertheless, the metagranitoids likely underwent significant geochemical changes during their metamorphic evolution including a severe loss of CaO and Na2O.
•First recognition of Ordovician metamorphism as the result of Cenerian orogeny in the Western Carpathians•Ordovician, Carboniferous and Cretaceous orogenic events revealed by monazite dating, mineral assemblages, P-T conditions•Polymetamorphosed metagranites with preserved magmatic and multiple metamorphic stages due to fluid-deficient conditions
The Variscan basement within the Western Carpathian Alpine architecture generally consists of metaluminous/peraluminous tonalite/granodiorite massifs and high-grade metamorphic complexes of ...metapelites, metaultramafites, and metabasites with relics of eclogites. Unfortunately, the Variscan crystalline basement of the Western Carpathians is only fragmentally exposed. Therefore, the proposed geodynamic evolutionary model for the Variscan granites of the Western Carpathians is primarily based on granite data from the Malá Fatra Mts. with additional dating from the High Tatra Mts. The oldest magmatic age of 362 ± 4 Ma in the Malá Fatra horst was recorded in diatexites from a high-grade metamorphic complex, which is related to crustal anatexis during Variscan subduction. Subsequent collisional event and break-off of the subducted slab promoted exhumation of the diatexites within the high grade metamorphic complex and intrusion of 353 ± 3 Ma old Tournaisian tonalite. Intensive heat input after slab break-off from the rising asthenosphere generated melting of the lower crust and extensive calc-alkaline, Mg-rich granitic magmatism in a short time span from 347 ± 4 to 342 ± 3 Ma. These Visean granitic rocks caused thermal overprint on the roof metamorphic rocks, including diatexites and Tournaisian tonalites at ca. 348 ± 5.6 to 342 ± 3 Ma. The Visean granite formation was controlled by the mixing of hot magmas, which is indicated by the presence of composite oligoclase/andesine plagioclase with preserved labradorite cores, alkali feldspars with Na2O ≥ 2 wt%, zoned apatite, the presence of antiperthite, and quartz ocelli. Elevated contents of mantle-derived elements like V, Ni, Cr, Ba, high Sr/Y ratio of ~44, steep LREE and flat HREE segments of chondrite-normalised patterns document adakite-like feature of the investigated granitic rocks which resulted from melting of a mixed lower-crustal and mantle sources and crystallisation in the presence of garnet. Unusual abundance of Fe–Ti oxides in granodiorites with magmatic cooling temperatures of 735–756 °C supports high-T input from mantle. In the High Tatra Mts., diorite xenolith shows the age of 359.2 ± 3 Ma, and its host granodiorite the age of 350.1 ± 2.6 Ma. The diorite contains acicular zircons, which points to rapid exhumation. Stubby zircon of the host granodiorite shows regular, oscillatory zoning controlled by a gradual temperature decrease. The non-comagmatic relationships between diorite and host granodiorite are indicated also by a difference in zircon Th/U ratio, which is 0.2 for the host granodiorite, but 1.0 for the diorite on average. The presented data show that slab break-off could have been a mechanism that promoted Variscan granitic magmatism in the Western Carpathians.
•Variscan subduction, slab break-off, exhumation and partial melting recorded in the Western Carpathians•Famennian (365-359 Ma), Tournaisian (359-353 Ma), and Visean (348–342 Ma) granitic magmatism recognised•Visean granites with adakitic signature derived from the melting of a mixed lower-crustal and mantle sources
Five crystals of pegmatitic xenotime from Ås II feldspar quarry (Evje, S Norway) were studied with comprehensive analytical methods from microscale to nanoscale with respect to fluid-mediated ...alterations and their geochronological implications. Xenotime crystals are strongly altered during dissolution-reprecipitation processes that resulted in the formation of (Th, U)-depleted xenotime subdomains with numerous microinclusions of (Th, U)-silicate, uraninite and minor galena. Remains of a primary xenotime (Xtm1) yielded LA-ICPMS UPb data characterized by a reverse discordance (from −10.5 to −2.6%) with a 208Pb/232Th mean age 988.4 ± 5.9 Ma (95% conf., MSWD = 0.75, n = 71), which is within uncertainty with a 207Pb/235U mean age 979.1 ± 5.0 Ma (95% conf., MSWD = 1.4, n = 22) yielded by data filtered to below ±5% discordance (i.e., from −5.0 to −2.6%). The altered xenotime domains (Xtm2) provided highly scattered dates, including 208Pb/232Th dates from 200 ± 14 to 2135 ± 120 Ma (n = 135). Discordant UPb data yielded upper intercept age 909 ± 16 Ma (MSWD = 7.9). EPMA Th-U-total Pb measurements and compositional characteristics of uraninite inclusions indicate three age populations of ca. 852–983, 594–687 and 37–101 Ma.
TEM investigations revealed initial alterations within domains Xtm1, representing a primary xenotime, which progressed along parallel submicron- to nanoscale fractures. These fractures represent partially open grain boundaries, which are empty or are filled with secondary inclusions of (Th, U)-silicates, uraninite or coffinite. The submicron-sized inclusions are accompanied by subdomains of (Th, U)-depleted xenotime. Altered xenotime (Xtm2) is well crystalline in TEM imaging and electron diffraction patterns in contrast to primary unaltered xenotime domains (Xtm1) that demonstrate, in Raman spectra, moderate degree of radiation damage caused by U and Th decay. Secondary inclusions of Th and U phases are nanocrystalline or amorphous, which increases their potential for Pb-loss or accumulation of Pb in excess. Some of them contain nanoinclusions of Pb3O4 or metallic Pb, whereas <100 nm-sized inclusions of (Pb, Sb)-oxide formed in the altered xenotime.
To summarize, this study provides important insights for our understanding of coupled dissolution-reprecipitation processes that affect xenotime and mobilization of released U, Th and Pb. Removal of highly mobile U in a fluid, and the presence of nanoinclusions of Pb3O4, (Pb, Sb)-oxide and metallic Pb have particular importance for xenotime dating and explain disturbance towards older ages. Nevertheless, both removal of U, Th and Pb from altered and recrystallized xenotime as well as presence of submicron- to nanoinclusions can result in age disturbance resulting in spread of dates along a concordia curve.
Fluid and mineral inclusions in metamorphic rocks allow the understanding of fluid-involved processes in subduction-zones providing essential contributions to the nature of geochemical processes and ...element cycling in present day subduction zones. In this work, we studied ultramafic granulite from the high-pressure (HP) and high-temperature (HT) metamorphic series of the Cabo Ortegal Complex, Spain, combining quartz-in-garnet and zircon-in-garnet Raman spectroscopy-based elastic geothermobarometry with Ti-in-quartz trace element thermometry. The studied quartz and zircon inclusions occur within garnet, together with rutile and multiphase fluid inclusions (MFI). Textural evidence, like occurrence in the same 3D cluster and common intergrowth of mineral inclusions, shows that both crystal inclusions and MFI were likely entrapped simultaneously. Hence, the application of elastic thermobarometry to quartz and zircon inclusions in these rocks provides excellent opportunity to define P-T environment of entrapment. Results from Raman spectroscopy on multiple quartz and zircon inclusions showed that the remnant elastic inclusion pressure (Pinc) at room conditions for both (on average 0.51 ± 0.04 GPa and 0.72 ± 0.05 GPa for the quartz and zircon inclusions, respectively) fall within the range of 2σ uncertainty confirming the crystallization within the same growth-stage of garnet. Intersection of the entrapment isomekes is at a P-T of 1.8 ± 0.2 GPa and 880 ± 70 °C. Electron microprobe measurements on quartz inclusions from the same garnet zone show uniform Ti concentrations (45–59 ppm). Isopleths calculated from Ti-in-quartz thermometer intersect the average quartz-in-garnet isomeke within the P-T range indicated by the intersection of quartz and zircon entrapment isomekes, which is P = 1.8 ± 0.2 GPa and T = 860 ± 70 °C.
Besides, we made a comparison of different reference materials applied for zircon-in-garnet elastic thermobarometry verified by independent Ti-in-quartz trace element thermometry. Our findings indicate that elastic thermobarometry on mineral inclusions provide a reliable constraint on the entrapment P-T conditions of coexisting fluid inclusions.
•Mineral and fluid inclusion entrapment at 1.8 ± 0.2 GPa, 870 ± 70 °C in granulite.•Combined use of zircon-in-garnet elastic and Ti-in-quartz trace element thermometry.•Quartz and zircon in garnet provide P-T entrapment data on fluid inclusions.•Elastic thermobarometry can be successfully combined with fluid inclusion studies.
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