Renata Čopjaková

Garnet as a major carrier of the Y and REE in the granitic rocks: An example from the layered anorogenic granite in the Brno Batholith, Czech Republic

Abstract Garnet and other rock-forming minerals from A-type granite dikes in the Pre-Variscan Brno Batholith were analyzed to determine relative contributions of individual minerals to whole-rock Y and REE budget and to assess incorporation mechanisms of these elements in garnet. Minor to accessory garnet (<2 vol%) is the essential reservoir for Y+REE in the Hlína granite accounting ∼84% Y and 61% REE of the total whole-rock budget. Zircon is another important carrier of REE with ∼13% Y and ∼11% REE. At least ∼21% REE and 1% Y were probably hosted by Th- and U-rich monazite that has been completely altered to a mixture of secondary REE-bearing phases. The contribution of major rockforming minerals (quartz and feldspars) is low (∼1% Y; 10% LREE; ∼1% HREE) excluding Eu, which is hosted predominantly by feldspars (∼90%). Minor to accessory muscovite and magnetite incorporate ∼1% Y and ∼2% REE of the whole-rock budget. Magmatic garnet Sps41-46Alm28-44And0-13 Grs6-12Prp0-1 is Y- and HREE-rich (up 1.54 wt% Y; up ∼1 wt% ΣREE), and the Y+REE enter the garnet structure via the menzerite-(Y) substitution. The Y and REE show complex zoning patterns and represent sensitive indicator of garnet evolution, in contrast to a homogeneous distribution of major divalent cations. General outward decrease of Y+REE is a common feature due to the strong partitioning of Y+HREE in the garnet relative to the other phases. REE underwent significant fractionation during growth of early garnet I; the YbN/NdN ratio generally decreases from the core to rim of garnet I. Higher Mn and Al, lower Ca, and Y+REE contents, as well as higher YbN/NdN ratio and more negative Eu anomaly in garnet II overgrowths indicate its crystallization from a more evolved melt. Application of zircon saturation geothermometry provides upper temperature limit of 734 ± 14 °C for the closed-system crystallization. Mineral equilibria reveal that crystallization started at QFM + 1.2, and preferential sequestration of Fe3+ into garnet and magnetite was responsible for progressively reducing conditions. Equilibrium between magnetite, garnet, quartz, and plagioclase, representing the final crystallization stage of the granitic magma, occurred at 658-663 °C and QFM 0 to + 0.8, hence at undercooling of ∼75 °C.

Sc- and REE-rich tourmaline replaced by Sc-rich REE-bearing epidote-group mineral from the mixed (NYF+LCT) Kracovice pegmatite (Moldanubian Zone, Czech Republic)

Abstract Primary black thick-prismatic Al-rich schorl to rare fluor-schorl (TurP1), locally overgrown by brownish-green Li-rich fluor-schorl to fluor-elbaite (TurP2) from the Kracovice pegmatite (mixed NYF+LCT signature), was partly replaced by secondary Li-rich fluor-schorl to fluor-elbaite (TurS) plus the assemblage REE-bearing epidote-group mineral + chamosite. Primary Al-rich schorl (TurP1) shows high and variable contents of Sc (33-364 ppm) and Y+REE (40-458 ppm) with steep, LREEenriched REE pattern. Overgrowing (TurP2) and replacing (TurS) Li-rich fluor-schorl to fluor-elbaite is typically depleted in Sc (21-60 ppm) and Y+REE (3-47 ppm) with well-developed tetrad effect in the first (La-Nd) and the second (Sm-Gd) tetrads. Scandium- and REE-rich black tourmaline (TurP1) crystallized earlier from the melt, whereas crystallization of primary Li-rich fluor-schorl to fluor-elbaite (TurP2) most likely took place during late magmatic to early hydrothermal conditions. Both the secondary Li-rich fluor-schorl to fluor-elbaite (TurS) and the unusual assemblage of REE-bearing epidotegroup mineral + chamosite are likely coeval products of subsolidus reactions of the magmatic Al-rich schorl (TurP1) with evolved REE-poor, Li,F-rich, alkaline pegmatite-derived fluids. Well-crystalline REE-bearing epidote-group mineral (Y+REE = 0.42-0.60 apfu) confirmed by Raman spectroscopy has a steep, LREE-rich chondrite-normalized REE pattern with significant negative Eu anomaly and shows variable and high contents of Sc (≤3.3 wt% Sc2O3) and Sn (≤1.0 wt% SnO2). Substitution ScAl-1 and minor vacancy in the octahedral sites are suggested in the REE-bearing epidote-group mineral.

Redefinition of thalénite-(Y) and discreditation of fluorthalénite-(Y): A re-investigation of type material from the Österby pegmatite, Dalarna, Sweden, and from additional localities

Abstract Using type material from the Österby pegmatite in Dalarna, Sweden, the chemical composition and structural parameters of thalénite-(Y) [ideally Y3Si3O10(OH)] were examined by wavelength dispersive spectroscopy electron microprobe (WDS EMP) analysis and single-crystal X-ray diffraction. High contrast back-scatter electron images of the Österby material show at least two generations of thalénite-(Y). The formula of the primary thalénite-(Y) normalized to 11 anions is (Y2.58Dy0.11Yb0.09Gd0.06Er0.06Ho0.02 Sm0.02Tb0.02Lu0.02Nd0.01Tm0.01)Σ3.00Si3.01O10F0.97OH0.03. The secondary thalénite-(Y), replacing the primary material, is weakly enhanced in Y and depleted in the lightest and the heaviest rare-earth elements, yielding the formula (Y2.63Dy0.12Yb0.06Gd0.06Er0.05Ho0.02Sm0.02Tb0.02Tm0.01Nd0.01Lu0.01)Σ3.00 Si3.01O10F0.98OH0.02. Structural data for thalénite-(Y) from Österby clearly indicate the monoclinic space group P21/n, with a = 7.3464(4), b = 11.1726(5), c = 10.4180(5) Å, β = 97.318(4)°, V = 848.13(7) Å3, Z = 4, which is consistent with previous investigations. The structure was refined from single-crystal X-ray diffraction data to R1 = 0.0371 for 1503 unique observed reflections, and the final chemical composition obtained from the refinement, (Y2.64Dy0.36)Σ3.00F0.987[Si3O10], Z = 4, is in good agreement with the empirical formula resulting from electron microprobe (EMP) analysis. Both techniques reveal a strong dominance of F over OH, which means that the type material actually corresponds to the fluorine analogue. Moreover, new EMP analyses of samples of thalénite-(Y) from an additional seven localities (Å skagen and Reunavare in Sweden; White Cloud and Snow Flake in Colorado, USA; the Guy Hazel claim in Arizona, USA; Suishoyama and Souri in Japan) clearly show the prevalence of F over OH as well. Based on these observations, the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association has recommended a redefinition of the chemical composition of thalénite-(Y) to represent the F-dominant species with the ideal formula Y3Si3O10F, as it has historical priority. Consequently, the later described fluorthalénite-(Y) has to be discredited.

Preparation and testing of phosphate, oxalate and uric acid matrix-matched standards for accurate quantification of 2D elemental distribution in kidney stone sections using 213 nm nanosecond laser ablation inductively coupled plasma mass spectrometry

Matrix-matched calibration for quantitative elemental mapping of kidney stones by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was developed with a 213 nm Nd:YAG laser ablation device and a quadrupole mass spectrometer. The method was applied to the imaging of P, Na, Sr, Zn, Ba and Pb distributions over a section of the kidney stone specimen containing phosphate and oxalate phases. Eighteen kidney stone specimens consisting of phosphate, oxalate and urate phases in various proportions were cut into halves for both preparation of calibration pellets and bulk analysis. Homogeneity of calibration pellets was examined by scanning electron microscopy (SEM) and LA-ICP-MS, concluding that areas of individual biominerals were thoroughly mixed and their size in units of micrometers was well below the size of the used laser spot. Calcium was employed as the internal reference element, being present in sufficient contents in the studied kidney stones. Mean values of calcium contents in oxalate and phosphate phases separately were determined using an electron microprobe (EMP) in the kidney stone section further subjected to the mapping. The actual (time- and space-resolved) Ca sensitivity was computed for each 44Ca+ signal and used as the internal reference for LA-ICP-MS isotopic signals of P, Na, Sr, Zn, Ba and Pb when mapping. Dependences of particular isotopic signal intensity/Ca sensitivity ratios vs. average elemental contents by solution analysis were processed by ordinary least squares linear regression. Despite variable matrices the regression yielded calibration lines with insignificant intercepts, coefficients of determination R2 > 0.9955, and relatively narrow prediction and confidence bands. However, in addition, the applicability of four-point calibration and four single-point calibrations as less time-consuming options was examined on the basis of the NIST SRM 1486 bone meal pellet analysis. Best fit was obtained for the four-point calibration and single-point calibration with the phosphate pellet. Quantitative elemental maps of the kidney stone section were recorded and computed for P, Na, Sr, Zn, Ba and Pb. The feasibility of quantification by matrix-matched single-point calibration was verified by determination of the median elemental contents in phosphate and oxalate phases by LA-ICP-MS and their arithmetic comparison mean values obtained over the same section area using EMP.